TWI693470B - Photosensitive resin composition, method for producing cured film, cured film, and liquid crystal display device - Google Patents

Abstract

A photosensitive resin composition comprising a polymer component A1 containing a polymer A1-1 and a photoacid generator B1, the polymer A1-1 comprising a group having an acid group protected by an acid-decomposable group Unit a1, and the photosensitive resin composition satisfies at least one of the following 1 to 3,

1: Polymer A1-1 further contains a structural unit a2 having a crosslinkable group

2: As polymer component A1, it further contains polymer A1-2, which contains a structural unit a2 having a crosslinkable group

3: It further contains a crosslinking agent C1 having a crosslinkable group and a molecular weight of 1,000 or less and satisfies at least one of the following 4 and 5.

4: The polymer A1-1 or the polymer A1-2 contains the structural unit represented by the following s1

5: As the polymer component A1, a polymer A1-3 containing a specific structural unit is further contained

Description

Photosensitive resin composition, method for manufacturing cured film, curing Film and liquid crystal display device

The present invention relates to a photosensitive resin composition, a method for manufacturing a cured film, a cured film, and a liquid crystal display device.

The liquid crystal display device has the advantages of thinness, light weight, and low power consumption, so it is widely used in various electronic devices.

In addition, a liquid crystal display device is usually provided with a patterned interlayer insulating film.

Regarding the formation of this interlayer insulating film, photosensitive resin compositions are widely used for the reason that the number of steps to obtain a desired pattern shape is small and sufficient flatness is obtained.

For example, Patent Document 1 describes, as a so-called chemically amplified photosensitive resin composition, "a photosensitive resin composition, which contains: (A-1) includes those satisfying the following (1) and (2) At least one of the polymer components of the polymer, (1) comprising (a1-1) a structural unit having an acid group protected by an acid-decomposable group and (a1-2) a structural unit having a crosslinkable group The polymer, or (2) has a composition The polymer of (a1-1) and the polymer having the structural unit (a1-2), (B-1) photoacid generator, and (C-1) solvent" ([claim 1]), in addition, As a naphthoquinonediazide (NQD) type photosensitive resin composition, "a photosensitive resin composition containing: (A-2) a structural unit having (a2-1) having an acid group and (a2-2) A polymer component having a structural unit having a crosslinkable group, (B-2) a quinonediazide compound, and (C-2) a solvent" ([claim 2]).

[Prior Art Literature]

[Patent Literature]

[Patent Literature 1] Japanese Patent Laid-Open No. 2014-197155

On the other hand, Patent Literature 1 describes a liquid crystal display device having a cured film obtained by curing a photosensitive resin composition as an interlayer insulating film ([0189] [0190]). In the known liquid crystal display device, in order to align liquid crystal molecules used in a liquid crystal cell, an alignment film must be provided on the interlayer insulating film.

Therefore, an object of the present invention is to provide a photosensitive resin composition capable of forming an interlayer insulating film that also serves as an alignment film, a method for manufacturing a cured film using the same, a cured film, and a liquid crystal display device.

The inventors of the present invention conducted intensive research in order to achieve the above-mentioned problems, and as a result, it was found that by arranging a polymer including a structural unit having a partial structure such as a fluorine-substituted hydrocarbon group and a structural unit having a photo-alignment group, it is possible to form dual alignment Interlayer The insulating film completes the present invention.

That is, it was found that the above-mentioned problems can be achieved by the following configuration.

[1] A photosensitive resin composition comprising a polymer component A1 containing a polymer A1-1 and a photoacid generator B1, the polymer A1-1 including a group having an acid group protected by an acid-decomposable group Constitutive unit a1, and the photosensitive resin composition satisfies at least one of the following 1 to 3,

1: The polymer A1-1 further includes a structural unit a2 having a crosslinkable group

2: As the polymer component A1, a polymer A1-2 is further included, and the polymer A1-2 includes a structural unit a2 having a crosslinkable group

3: It further contains a crosslinking agent C1 having a crosslinkable group and a molecular weight of 1,000 or less and satisfies at least one of the following 4 and 5.

4: The polymer A1-1 or the polymer A1-2 contains the structural unit represented by the following s1

5: As the polymer component A1, a polymer A1-3 containing a structural unit represented by the following s1 is further contained

s1: a structural unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton, and a C10-30 alkyl group, and a structural unit having a photo-alignment group

[2] The photosensitive resin composition according to [1], wherein the acid group is protected by an acid-decomposable group, and the acid group is protected in the form of an acetal.

[3] A photosensitive resin composition comprising a polymer component A2 containing a polymer A2-1 and a quinonediazide compound B2, the polymer A2-1 containing an acid Based structural unit a3, and the photosensitive resin composition satisfies at least one of the following 1 to 3,

1: The polymer A2-1 further includes a structural unit a2 having a crosslinkable group

2: The polymer component A2 further contains a polymer A2-2, and the polymer A2-2 includes a structural unit a2 having a crosslinkable group

3: It further contains a crosslinking agent C2 having a crosslinking group and a molecular weight of 1,000 or less

And at least one of the following 4 and 5 is satisfied.

4: The polymer A2-1 or the polymer A2-2 contains the structural unit represented by the following s1

5: The polymer component A2 further contains a polymer A2-3 containing a structural unit represented by the following s1

s1: a structural unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton, and a C10-30 alkyl group, and a structural unit having a photo-alignment group

[4] The photosensitive resin composition as described in any one of [1] to [3], wherein the photo-alignment group is a group that imparts alignment by photodimerization reaction.

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the photo-alignment group is a cinnamate group or a chalcone group.

[6] The photosensitive resin composition according to any one of [1] to [5], wherein the crosslinkable group is an epoxy group or an oxetanyl group.

[7] The photosensitive resin composition according to any one of [1] to [6], wherein the polymer has the structural unit represented by s1 relative to the total solid content of the composition The content is 0.1% by mass to 20% by mass.

[8] The photosensitive resin composition according to any one of [1] to [7], which contains an organic solvent D.

[9] A method for manufacturing a cured film, comprising: a step of applying the photosensitive resin composition as described in [8] on a substrate; and a step of removing the organic solvent D from the applied photosensitive resin composition A step of exposing the photosensitive resin composition from which the organic solvent D has been removed by active radiation; a step of developing the exposed photosensitive resin composition with a developing solution; and a step of developing the photosensitive resin composition The step of heat curing to obtain a cured film.

[10] A cured film obtained by curing the photosensitive resin composition according to any one of [1] to [8].

[11] A liquid crystal display device having the cured film as described in [10].

According to the present invention, it is possible to provide a photosensitive resin composition capable of forming an interlayer insulating film that also serves as an alignment film, a method for manufacturing a cured film using the same, a cured film, and a liquid crystal display device.

Hereinafter, the present invention will be described in detail.

The description of the constituent elements described below may be based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.

In addition, in this specification, the numerical range shown using "~" means the range including the numerical value described before and after "~" as a lower limit and an upper limit.

In the description of the group (atomic group) in the present specification, the description that does not describe substituted and unsubstituted includes a group (atomic group) having no substituent, and also includes a group (atomic group) having a substituent. For example, the so-called "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group), but also an substituted alkyl group (substituted alkyl group).

In this specification, "(meth)acrylate" means "acrylate" or "methacrylate", and "(meth)acrylic acid" means "acrylic acid" or "methacrylic acid". "(Meth)acryloyl" refers to "acryloyl" or "methacryloyl".

In this specification, the solid content is the solid content at 25°C.

In this specification, the weight-average molecular weight and number-average molecular weight of the polymer are defined as polystyrene conversion values measured by a gel permeation chromatography (Gel Permeation Chromatograph, GPC).

The photosensitive resin composition of the first aspect of the present invention (hereinafter also simply referred to as "the first aspect of the present invention") is a photosensitive resin composition including the polymer component A1 containing the polymer A1-1 , And a photoacid generator B1, the polymer A1-1 includes a structural unit a1 having a group protected by an acid-decomposable acid group, and the The photosensitive resin composition satisfies at least one condition shown in 1 to 3 described later, and satisfies at least one condition shown in 4 and 5 described later.

In addition, the photosensitive resin composition of the second aspect of the present invention (hereinafter also simply referred to as "the second aspect of the present invention") is a photosensitive resin composition that includes a polymer containing a polymer A2-1 Component A2, and a quinonediazide compound B2, the polymer A2-1 includes a structural unit a3 having an acid group, and the photosensitive resin composition satisfies at least one of the conditions shown in 1 to 3 described below, and satisfies at least A condition shown in 4 and 5 described later.

The photosensitive resin composition of the first aspect and the second aspect of the present invention can form an interlayer that also serves as an alignment film by blending a polymer having a structural unit represented by s1 described later as the polymer component A1 or the polymer component A2. Insulating film.

Although the details are not clear, the present inventors presume as follows.

That is, a polymer having a structural unit shown in s1 described later includes both a structural unit having a photo-alignment group and a structural unit having a partial structure such as a fluorine-substituted hydrocarbon group, whereby the resin composition is applied to a substrate (such as a thin film After the transistor, etc.), the polymer containing the structural unit having a photo-alignment group is transferred (bleed) to the vicinity of the surface of the coating film, so that the photo-alignment group tends to exist near the surface of the cured film after thermal curing Therefore, it is considered to function as an alignment film (optical alignment film).

Next, each component such as the polymer component used in the first aspect and the second aspect of the present invention will be described in detail.

[The first aspect of the present invention]

The first aspect of the present invention contains the following polymer component A1 and a photoacid generator B1.

[Polymer component A1]

The polymer component A1 contained in the first aspect of the present invention is a polymer component containing a polymer A1-1 including a structural unit a1 having a group having an acid group protected by an acid-decomposable group .

Here, regarding the polymer component A1, the deprotection reaction of the acid-decomposable group in the polymer A1-1 proceeds due to the action of an acidic substance in the amount of catalyst generated by the photoacid generator B1 described later. Acid group, by which the hardening reaction can proceed.

In addition, the polymer component A1 refers to those that include other polymers added as necessary in addition to the above-mentioned polymer A1-1.

In the present invention, the polymer contained in the polymer component A1 is preferably an addition polymerization type polymer, and more preferably a polymer containing a structural unit derived from (meth)acrylic acid and/or its ester.

Moreover, you may have a structural unit other than a structural unit derived from (meth)acrylic acid and/or its ester, for example, a structural unit derived from styrene, a structural unit derived from a vinyl compound, etc.

In addition, "the structural unit derived from (meth)acrylic acid and/or its ester" is also called "acrylic structural unit."

The first aspect of the present invention must satisfy at least one of the conditions shown in 1 to 3 below, and must satisfy at least one of the conditions shown in 4 and 5 below.

This means that in the polymer A1-1 containing the structural unit a1 having an acid group protected by an acid-decomposable group, or separated from the polymer A1-1, it is necessary to have a contribution The part or component of the hardened crosslinkable group; and the polymer component which must include a structural unit having a photo-alignment group and a structural unit for biasing it to exist on the surface.

Therefore, in the following description, the structural units in the polymer necessary as a polymer component are mainly described, not for each polymer.

(condition)

1: The polymer A1-1 further includes a structural unit a2 having a crosslinkable group

2: As the polymer component A1, a polymer A1-2 is further included, and the polymer A1-2 includes a structural unit a2 having a crosslinkable group

3: It further contains a crosslinking agent C1 having a crosslinkable group and a molecular weight of 1,000 or less

4: The polymer A1-1 or the polymer A1-2 contains the structural unit represented by the following s1

5: As the polymer component A1, a polymer A1-3 containing a structural unit represented by the following s1 is further contained

s1: a structural unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton, and a C10-30 alkyl group, and a structural unit having a photo-alignment group

<Construction unit a1>

The polymer component A1 includes a polymer A1-1 including at least a structural unit a1 having a group in which an acid group is protected by an acid-decomposable group. When the polymer component A1 includes the polymer A1-1 having the structural unit a1, a chemically amplified resin composition with extremely high sensitivity can be produced.

The "acid group protected by an acid-decomposable group" in the present invention can be used as Those known as acid groups and acid-decomposable groups are not particularly limited.

As an acid group, a carboxyl group, a phenolic hydroxyl group, etc. are mentioned preferably, for example.

In addition, examples of the acid-decomposable group include groups that are relatively easily decomposed by acid (for example, acetal-based functional groups such as an ester structure, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group described later), or relatively difficult A group decomposed by acid (for example, tertiary alkyl group such as tertiary butyl ester group, tertiary alkyl carbonate group such as tertiary butyl carbonate group), etc.

The structural unit a1 having a group having an acid group protected by an acid-decomposable group is preferably a structural unit having a protected carboxyl group having a carboxyl group protected by an acid-decomposable group (hereinafter also referred to as "having a protected carboxyl group protected by an acid-decomposable group" "Constitutional unit"), or a constitutional unit having a phenolic hydroxyl group protected by an acid-decomposable group and a protected phenolic hydroxyl group (hereinafter also referred to as "a constitutional unit having a protected phenolic hydroxyl group protected by an acid-decomposable group").

Hereinafter, the structural unit a1-1 having a protected carboxyl group protected with an acid-decomposable group and the structural unit a1-2 having a protected phenolic hydroxyl group protected with an acid-decomposable group will be sequentially described below.

<<Constitutional unit having a protected carboxyl group protected with an acid-decomposable group a1-1>>

The structural unit a1-1 having a protected carboxyl group protected with an acid-decomposable group is a structural unit including a protective carboxyl group having a carboxyl group having a carboxyl group-protected unit protected by an acid-decomposable group described in detail below.

As the structural unit having a carboxyl group that can be used in the structural unit a1-1 having a protected carboxyl group protected with an acid-decomposable group, a known structural unit can be used without particular limitation. Examples include unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and A structural unit a1-1-1 such as an unsaturated carboxylic acid having at least one carboxyl group in a molecule such as a saturated tricarboxylic acid, or a structural unit a1-1-2 having a structure derived from an ethylenic unsaturated group and an acid anhydride at the same time.

In the following, a1-1-1 used as the structural unit having the carboxyl group is derived from a structural unit such as an unsaturated carboxylic acid having at least one carboxyl group in the molecule, and a-1-1-2 has both ethylenic properties The unsaturated group and the structural unit derived from an acid anhydride structure are described separately.

<<<Structural unit a1-1-1 derived from unsaturated carboxylic acid having at least one carboxyl group in the molecule>>>

Examples of the unsaturated carboxylic acid used in the present invention regarding the structural unit a1-1-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule include, for example, Japanese Patent Laid-Open No. 2014-238438 The compound described in paragraph 0043.

Among them, from the viewpoint of developability, in order to form the structural unit a1-1-1, it is preferable to use acrylic acid, methacrylic acid, 2-(meth)acryloxyethyl-succinic acid, 2- (Meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl-phthalic acid, or anhydride of unsaturated polycarboxylic acid, etc., preferably acrylic acid , Methacrylic acid, 2-(meth)acryloxyethyl hexahydrophthalic acid.

The structural unit a1-1-1 derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule may contain a single kind or two or more kinds.

<<<Constitutional unit a1-1-2 having both an ethylenically unsaturated group and a structure derived from acid anhydride>>>

Constituent unit having both an ethylenically unsaturated group and a structure derived from acid anhydride a1-1-2 is preferably a unit derived from a monomer obtained by reacting a hydroxyl group present in a structural unit having an ethylenically unsaturated group with an acid anhydride.

As the acid anhydride, known ones can be used, and specific examples include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorobridge anhydride Such as dibasic acid anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, biphenyltetracarboxylic anhydride and other anhydrides. Among these acid anhydrides, from the viewpoint of developability, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferred.

From the viewpoint of developability, the reaction rate of the acid anhydride to the hydroxyl group is preferably 10 mol% to 100 mol%, more preferably 30 mol% to 100 mol%.

(Acid-decomposable group that can be used to constitute unit a1-1)

As the acid-decomposable group that can be used for the structural unit a1-1 having the protected carboxyl group protected with an acid-decomposable group, the acid-decomposable group can be used.

Among these acid-decomposable groups, from the viewpoint of the basic physical properties of the resin composition, particularly from the viewpoints of sensitivity or pattern shape, formation of contact holes, and storage stability of the resin composition, the carboxyl group is preferably acetal The protected carboxyl group is protected in form. Furthermore, from the viewpoint of sensitivity, in the acid-decomposable group, it is more preferable that the carboxyl group is a protected carboxyl group which is protected in the form of an acetal represented by the following formula a1-10. In addition, when the carboxyl group is a protected carboxyl group represented by the following formula a1-10 and protected in the form of an acetal, the entire protected carboxyl group becomes -(C=O)-O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ )Structure.

[Chemical 1]

In formula a1-10, R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or a hydrocarbon group, except that R ¹⁰¹ and R ^{102 are} both hydrogen atoms. R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to form a cyclic ether.

In the formula a1-10, R ¹⁰¹ to R ¹⁰³ each independently represent a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched, or cyclic. Here, there is no case where both R ¹⁰¹ and R ¹⁰² represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

In the formula a1-10, when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an alkyl group, the alkyl group may be any of linear, branched or cyclic.

The straight-chain or branched-chain alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, n-pentyl, neopentyl, n-hexyl, and third hexyl (thexyl) (2,3-dimethyl-2-butyl), n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc.

The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and even more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, and isobornyl.

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When a halogen atom is used as a substituent, R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ are haloalkyl groups, and when an aryl group is used as a substituent, R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ are aralkyl groups.

Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, and iodine atom. Among these halogen atoms, a fluorine atom or a chlorine atom is preferred.

In addition, the aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Specific examples include phenyl, α-methylphenyl, and naphthyl. As the entire alkyl group substituted with an aryl group, that is, an aralkyl group, examples include benzyl, α-methylbenzyl, phenethyl, and naphthyl. Methyl and so on.

The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and further preferably a methoxy group or an ethoxy group.

In addition, when the alkyl group is a cycloalkyl group, the cycloalkyl group may also have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group may be linear Or in the case of a branched chain alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent.

These substituents may be further substituted by the substituents.

In the formula a1-10, when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The aryl group may have a substituent. As the substituent, an alkyl group having 1 to 6 carbon atoms can be preferably exemplified. Examples of the aryl group include phenyl, tolyl, xylyl, cumenyl, and 1-naphthyl.

In addition, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may be bonded to each other to form a ring together with these bonded carbon atoms or oxygen atoms. Examples of the ring structure when R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ^103, or R ¹⁰² and R ^{103 are} bonded include, for example, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, tetrahydrofuranyl, and adamantane Alkyl and tetrahydropyranyl etc.

Furthermore, in the above formula a1-10, it is preferable that either of R ¹⁰¹ and R ¹⁰² is a hydrogen atom or a methyl group.

The radically polymerizable monomer used to form the structural unit having the protected carboxyl group represented by the above formula a1-10 may use a commercially available product, or may be synthesized by a known method. For example, it can be synthesized by the synthesis method described in paragraphs 0037 to 0040 of Japanese Patent Laid-Open No. 2011-221494.

The first preferred aspect of the structural unit a1-1 having the protected carboxyl group protected by an acid-decomposable group is a structural unit represented by the following formula.

In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ¹ and R ² is an alkyl group or an aryl group, R ³ represents an alkyl group or an aryl group, R ¹ Or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an aryl group.

When R ¹ and R ² are alkyl groups, it is preferably an alkyl group having 1 to 10 carbon atoms. When R ¹ and R ² are aryl groups, phenyl is preferred. R ¹ and R ² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R ³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.

X represents a single bond or an aryl group, preferably a single bond.

The second preferred aspect of the structural unit a1-1 having the protected carboxyl group protected by an acid-decomposable group is a structural unit represented by the following formula.

In the formula, R ¹²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenylene group, and R ¹²² to R ¹²⁸ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R ^{121 is} preferably a hydrogen atom or a methyl group.

L ^{1 is} preferably a carbonyl group.

R ¹²² to R ^{128 are} preferably hydrogen atoms.

As a preferable specific example of the structural unit a1-1 having the protected carboxyl group protected by an acid-decomposable group, the following structural units can be exemplified. In addition, R represents a hydrogen atom or a methyl group.

<<Constitutional unit having a phenolic hydroxyl group protected with an acid-decomposable group a1-2>>

Examples of the structural unit a1-2 having a phenolic hydroxyl group protected with an acid-decomposable group include a hydroxystyrene-based structural unit or a novolac-based resin.

Among these structural units, from the viewpoint of sensitivity, a structural unit derived from hydroxystyrene or α-methylhydroxystyrene is preferred.

In addition, the structural unit having a phenolic hydroxyl group is also preferably the structural unit described in paragraphs 065 to 0007 of Japanese Patent Laid-Open No. 2014-238438 from the viewpoint of sensitivity.

(Preferable form of constituent unit a1)

When the polymer having the structural unit a1 does not substantially have the following structural unit a2, the structural unit a1 is preferably 20 mol% to 100 mol% in the polymer having the structural unit a1 , More preferably 30 mol% to 90 mol%.

In the case where the polymer having the structural unit a1 has the following structural unit a2, from the viewpoint of sensitivity, the structural unit a1 is preferably 3 in the polymer having the structural unit a1 and the structural unit a2 Molar% ~ 70 mol%, more preferably 10 mol% ~ 60 mol%. In addition, in particular, when the structural unit a1 is a structural unit having a protected carboxyl group whose carboxyl group is protected in the form of an acetal, it is preferably 20 mol% to 50 mol%.

In addition, in the present invention, when the content of the "constituent unit" is specified in terms of molar ratio, "constituent unit" and "monomer unit" have the same meaning. In addition, in the present invention, the "monomer unit" may be modified after polymerization by polymer reaction or the like. The following is also the same.

The structural unit a1-1 having a protected carboxyl group protected by an acid-decomposable group has a characteristic of rapid development compared with the structural unit a1-2 having a protected phenolic hydroxyl group protected by an acid-decomposable group. Therefore, in the case of rapid development, it is preferable to have a structural unit a1-1 having a protected carboxyl group protected by an acid-decomposable group. Conversely, in the case where development is to be performed slowly, it is preferable to use the structural unit a1-2 having a protected phenolic hydroxyl group protected with an acid-decomposable group.

<Construction unit a2>

The polymer component A1 preferably contains a polymer containing a structural unit a2 having a crosslinkable group. Moreover, as shown in the conditions 1 to 3 In general, when the crosslinking agent C1 described below is not included, the polymer A1-1 containing at least the structural unit a1 having a group having an acid group protected by an acid-decomposable group must further include a structural unit having a crosslinkable group a2; or must contain another polymer A1-2, which contains a structural unit a2 having a crosslinkable group.

The crosslinkable group is not particularly limited as long as it causes a hardening reaction by heat treatment.

Preferred aspects of the structural unit having a crosslinkable group include those selected from epoxy groups, oxetanyl groups, -NH-CH ₂ -OR (R represents a hydrogen atom or carbon number 1 ~20 alkyl group) at least one kind of structural unit of the group represented by the group represented by the ethylenically unsaturated group, and blocked isocyanate group, preferably contains a group selected from the group consisting of epoxy group and oxetanyl group , -NH-CH ₂ -OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), at least one of the group consisting of a (meth)acryloyl group and a blocked isocyanate group The structural unit of is more preferably composed of a group selected from the group consisting of epoxy groups, oxetanyl groups, and -NH-CH ₂ -OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) At least one constituent unit of the group.

<<Structural unit having a epoxy group and/or oxetanyl a2-1>>

The polymer component A1 preferably contains a polymer including the structural unit a2-1 having an epoxy group and/or oxetanyl group. Moreover, the cyclic ether group of a three-membered ring is also called an epoxy group, and the cyclic ether group of a four-membered ring is also called an oxetanyl group.

The structural unit a2-1 having an epoxy group and/or oxetanyl group only needs to have at least one epoxy group or oxetanyl group in one structural unit, and may have one or more rings Oxygen and one or more oxetanyl groups, two or more epoxy groups, or Two or more oxetanyl groups are not particularly limited, but preferably have a total of 1 to 3 epoxy groups and/or oxetanyl groups, more preferably have a total of 1 or 2 epoxy groups And/or oxetanyl, and more preferably one epoxy group or oxetanyl group.

Specific examples of the radically polymerizable monomer used to form the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, and α- N-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, -3,4-epoxybutyl acrylate, methacrylate-3,4-epoxybutyl, acrylate-3,4-epoxy Cyclohexyl methyl ester, methacrylic acid-3,4-epoxycyclohexyl methyl ester, α-ethyl acrylic acid-3,4-epoxycyclohexyl methyl ester, o-vinyl benzyl glycidyl ether, m-vinyl benzyl Glycidyl ether, p-vinylbenzyl glycidyl ether, compounds containing an alicyclic epoxy skeleton described in paragraphs 0031 to 0035 of Japanese Patent No. 4168443, the contents of which are incorporated into this application In the manual.

Specific examples of the radically polymerizable singular body used to form the structural unit having an oxetanyl group include, for example, paragraphs 0011 to 0016 described in Japanese Patent Laid-Open No. 2001-330953 Butyl (meth)acrylate, etc., these contents are incorporated in the specification of this application.

As a specific example of the radically polymerizable singular body for forming the structural unit a2-1 having the epoxy group and/or oxetanyl group, a monomer containing a methacrylate structure, containing Monomer of acrylic structure.

Among these, glycidyl methacrylate, -3,4-epoxycyclohexyl methyl acrylate, -3,4-epoxycyclohexyl methyl methacrylate, acrylic acid (3-ethyl Oxetan-3-yl) methyl ester, and (3-ethyloxetan-3-yl) methyl methacrylate. These constituent units may be used alone or in combination of two or more.

As a preferable specific example of the structural unit a2-1 having an epoxy group and/or oxetanyl group, the following structural units can be exemplified. In addition, R represents a hydrogen atom or a methyl group.

<<Constitution unit with ethylenically unsaturated group a2-2>>

As another example of the structural unit a2 having the crosslinkable group, a structural unit a2-2 having an ethylenically unsaturated group may be mentioned. The structural unit a2-2 having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group on the side chain, and more preferably has an ethylenically unsaturated group at the terminal and has a carbon number of 3 Constituent unit of ~16 side chain.

In addition, regarding the structural unit a2-2 having an ethylenically unsaturated group, reference can be made to the description of paragraphs 072 to 0090 of Japanese Patent Laid-Open No. 2011-215580, and paragraph 0013 to the Japanese Patent Laid-Open No. 2008-256974 The description in paragraph 0031 incorporates these contents into the specification of the present application.

<<Constitution unit a2-3 having a group represented by -NH-CH ₂ -OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms)>>

As another example of the structural unit a2 having the crosslinkable group, it is also preferable to have a structure represented by —NH—CH ₂ —OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). Unit a2-3. By having the constituent unit a2-3, a slow heat treatment can be used to cause a hardening reaction, and a cured film having excellent characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 9 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms. In addition, the alkyl group may be any of linear, branched, or cyclic alkyl groups, and preferably linear or branched alkyl groups. The structural unit a2-3 is more preferably a structural unit having a group represented by the following formula a2-30.

In formula a2-30, R ³¹ represents a hydrogen atom or a methyl group, and R ³² represents an alkyl group having 1 to 20 carbon atoms.

R ^{32 is} preferably an alkyl group having 1 to 9 carbons, and more preferably an alkyl group having 1 to 4 carbons. In addition, the alkyl group may be any of linear, branched, or cyclic alkyl groups, and preferably linear or branched alkyl groups.

Specific examples of R ³² include methyl, ethyl, n-butyl, isobutyl, cyclohexyl, and n-hexyl. Among them, isobutyl, n-butyl, and methyl are preferred.

(Preferable form of constituent unit a2)

When the polymer having the structural unit a2 does not have the structural unit a1, the structural unit a2 is preferably 5 mol% to 90 mol% in the polymer having the structural unit a2, more preferably 20 mol% to 80 mol%.

When the polymer having the structural unit a2 has the structural unit a1, the content of the structural unit a2 in the polymer having the structural unit a1 and the structural unit a2 is preferably 1 mol% to 70 mol %, more preferably 3 mol% to 60 mol%.

In the present invention, regardless of any of the forms, it is preferable to include the structural unit a2 of 0 mol% to 70 mol% in all the structural units of the polymer component A1, and more preferably to contain 0 mol% to 50 mol ear%. In addition, as described above, when the content of the constituent unit a2 is 0 mol %, it is necessary to contain the crosslinking agent C1 described later.

If it is within the range of the above-mentioned numerical value, the etching resist residue on the surface of the cured film after peeling off the etching resist on the inorganic film deposited in the subsequent step of the cured film obtained from the resin composition becomes small and becomes good.

<Construction unit shown in s1>

The polymer component A1 contains a polymer including the structural unit represented by the following s1 (hereinafter also referred to as "constituent unit s1"). Furthermore, as shown in the above conditions 4 and 5, the structural unit s1 may be (A) The polymer A1-1 including the structural unit a1 having at least an acid group protected by an acid-decomposable group has a constitution Aspect of the unit s1; (B) another polymer A1-2 including the constitutional unit a2 having a crosslinkable group further has the aspect of the constitutional unit s1; and (C) another polymer A1-3 has a constitutional unit s1 Any of the appearances.

s1: a structural unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton, and an alkyl group having 10 to 30 carbon atoms (hereinafter also referred to as "bias-existing group"), and Constituent unit with photo-alignment group

<<Constitutional unit having a partial structure of a fluorine-substituted hydrocarbon group>>

The fluorine-substituted hydrocarbon group may be a hydrocarbon group substituted with at least one fluorine atom, and examples thereof include an alkyl group or an alkylene group (hereinafter, abbreviated as "alkyl group" in this paragraph) in which at least one hydrogen atom is substituted with a fluorine atom. The alkyl group and the like are more preferably an alkyl group in which all hydrogen atoms of the alkyl group and the like are substituted with fluorine atoms.

From the viewpoint of preference for existence, such a fluorine-substituted hydrocarbon group is preferably a group represented by the following general formula I.

In the general formula I, R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a connection site to the polymer chain. X represents a single bond or a divalent linking group, m represents an integer of 1 to 3, n represents an integer of 1 or more, and r represents an integer of 0 or 1 to 2. In addition, when m is 1, a plurality of R ² may be the same or different.

M in the general formula I represents an integer of 1 to 3, preferably 1 or 2.

N in the general formula I represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and particularly preferably 1 or 2.

In the general formula I, r represents 0 or an integer of 1 to 2, preferably 1 or 2, and more preferably 2.

In addition, the connection site to the polymer chain represented by * may be directly bonded to the main chain of the polymer such as the polymer A1-1, or via polyoxyalkylene, alkylene, ester group, amine group The formate group may be bonded with a divalent linking group such as a cyclic alkylene group containing a hetero atom, poly(caprolactone), or an amine group. It is preferably bonded via polyoxyalkylene.

In the general formula I, examples of the alkyl group having 1 to 4 carbon atoms represented by R ² include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and third butyl The group and the like are preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

In the general formula I, the case where X is a single bond means that the polymer main chain is directly connected to the carbon atom to which R ² is bonded.

In addition, when X is a divalent linking group, examples of the linking group include -O-, -S-, -N(R ⁴ )-, -CO-, and the like. Among these, -O- is more preferable. Here, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a third butyl group, and a hydrogen atom and a methyl group are preferred.

Examples of a method for introducing a fluorine-substituted hydrocarbon group into a polymer include: a method for introducing a fluorine-substituted hydrocarbon group into a polymer through a polymer reaction; and a monomer having a fluorine-substituted hydrocarbon group (hereinafter referred to as a "fluorine-substituted hydrocarbon group-containing monomer" "Body") copolymerization, and Yu polymerization A method of introducing a structural unit having a fluorine-substituted hydrocarbon group into the compound.

Examples of the fluorine-substituted hydrocarbon group-containing monomer in the method of copolymerizing a fluorine-substituted hydrocarbon group-containing monomer and introducing a structural unit having a fluorine-substituted hydrocarbon group into a polymer include monomers represented by the following general formula II as Better.

In Formula II, R ¹ represents a hydrogen atom, a halogen atom, a methyl group which may have a substituent, or an ethyl group which may also have a substituent. Further, R ^2, X, m, n and r have the general formula I is R ^2, X, m, n and r have the same meaning as the preferred embodiments are also the same.

In addition, in the general formula II, examples of the halogen atom represented by R ¹ include a fluorine atom, a chlorine atom, and a bromine atom.

Furthermore, regarding the production method of such a fluorine-substituted hydrocarbon group-containing monomer, for example, on pages 117 to 118 of "Synthesis and Function of Fluorine Compounds" (Editor: Yanshi Ishikawa, Issue: CMC Co., Ltd., 1987), or "Chemistry of Organic Fluorine Compounds II" (Monograph) 187, Milos Hudlicky and Attila E. Pavlath (Attila E. Pavlath), American Chemical Society (American Chemical Society) 1995 pages 747 ~ 752 are described.

In addition, specific examples of the monomer represented by the general formula II include tetrafluoroisopropyl methacrylate represented by the following formula IIa, hexafluoroisopropyl methacrylate represented by the following formula IIb, and the like.

In addition, as other specific examples, the compounds described in paragraph numbers [0058] to paragraph numbers [0061] of Japanese Patent Laid-Open No. 2010-18728 can be cited. Among these, a structure in which a fluorine-substituted hydrocarbon group is bonded to a polyoxyalkylene group is preferred.

<<Construction unit with partial structure of siloxane skeleton>>

The siloxane skeleton is not particularly limited as long as it has "-Si-O-Si-", and it preferably contains polyoxyalkylene.

In the present invention, regarding the siloxane skeleton, it is preferable to copolymerize a compound having (meth)acryloyloxy and alkoxysilyl groups from the viewpoint of preference for existence In combination, a structural unit having a partial structure of a siloxane skeleton is introduced into the polymer.

Here, the alkoxysilane group is preferably a group represented by the following formula (X), for example.

In the formula (X), R ³ to R ⁵ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, or an alkoxy group, and at least one of them is an alkoxy group. * Indicates the bonding position.

In the formula (X), at least one of R ³ to R ⁵ is an alkoxy group, and as the alkoxy group, preferably an alkoxy group having 1 to 15 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms The oxy group is further preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably an ethoxy group or a methoxy group.

In the present invention, it is preferable that two of R ³ to R ⁵ are alkoxy groups and one is an alkyl group, or three are alkoxy groups. Among them, three are preferably alkoxy groups, that is, trialkoxysilyl groups.

Examples of such a compound having an alkoxysilane group and (meth)acryloyloxy group include, for example, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3 -(Meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropyltriethyl Oxysilicon Alkane etc.

In addition, in the present invention, the siloxane skeleton is preferably a compound represented by the following structural formula (A) (hereinafter also referred to as "specific siloxane compound") from the viewpoint of preference for existence. Polymerization, and the silicone skeleton is introduced into the polymer.

In the structural formula (A), R ⁷ represents a linear or branched alkylene group having 2 to 6 carbon atoms, which may have a substituent such as a hydroxyl group, an amine group, a halogen atom, or the following structural formula (B) Represents a divalent linking group.

In the structural formula (B), R ⁴ represents a hydrogen atom, a methyl group, and an ethyl group. n1, n2, and n3 are each independently an integer of 0-100. Here, there are two or more R ⁴ in the structural formula (B), which may be different from each other, or may be the same.

In the structural formula (A), x1, x2, and x3 are the total of these An integer from 1 to 100.

In addition, y1 is an integer of 1-30.

In the structural formula (A), X ² is a single bond or a divalent group represented by the following structural formula (C).

In the structural formula (C), R ⁸ represents a linear or branched alkylene group having 1 to 6 carbon atoms which may have a substituent such as a hydroxyl group, an amine group, a halogen atom, and Q ¹ and Q ² represent an oxygen atom , Sulfur atom, or -NRB-, Q ¹ and Q ² may be different from each other, and may also be the same. RB represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the structural formula (C), Q ^{2 is} bonded to R ⁷ in the structural formula (A).

In the structural formula (A), Y ² represents a monovalent group represented by the following structural formula (D) to the following structural formula (F).

[化14]

In the structural formula (D) to the structural formula (F), R ⁵ represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.

In the structural formula (A), Z ¹ , Z ² , and Z ³ each independently represent a monovalent group represented by the following structural formula (G).

In the structural formula (G), R ⁶ represents an unsubstituted alkyl group having 1 to 4 carbon atoms, and y ² represents an integer of 1 to 100, preferably an integer of 1 to 50, and more preferably 1 to 20 Integer.

In addition, as the siloxane skeleton, the structures described in paragraph number [0092] to paragraph number [0094] of Japanese Patent Laid-Open No. 2010-18728 can be cited as specific examples of the above formula (A), but it is not limited For those.

Among these, the structure in which the siloxane structure is bonded to the polymer via polyoxyalkylene is preferred.

<<Constitutional unit having an alkyl moiety structure having 10 to 30 carbon atoms>>

The alkyl group having a carbon number of 10 to 30 may also include a branched structure or a cyclic structure. It is preferable that the carbon number of the linear structure part is in the range of 10 to 30, and it is more preferable that all of the linear structure is a linear structure.

In addition, the carbon number of the alkyl group is preferably 10-20.

Specifically, it is preferable that the side chain of the polymer has a group represented by the following general formula (a3-1).

In the general formula (a3-1), n _a3 represents an integer of 10 to 30, and * represents a position connected to the main chain or side chain of the polymer. n _{a3 is} preferably an integer of 10-20.

The method of introducing the structure of the general formula (a3-1) into the main chain or side chain of the polymer is not particularly limited, for example, as long as the monomer having the structure of (a3-1) is appropriately selected and applied during synthesis, Then, the structure of (a3-1) can be introduced into the repeating unit of the obtained polymer.

In addition, as the monomer having the structure of the general formula (a3-1), a commercially available compound may be used, or a commercially available monomer having no structure (a3-1) may be appropriately introduced into (a3-1) Use the desired structure contained in it. The method of introducing the structure of (a3-1) into a commercially available monomer is not limited, as long as a known method is appropriately applied.

The monomer having the structure of the general formula (a3-1) can be appropriately selected according to the main chain structure of the polymer. For example, if it is a polymer having a (meth)acrylic structure on the main chain, it is preferably used as follows The monomer represented by the general formula (a3-2).

In the general formula (a3-2), R ³² represents a hydrogen atom, a methyl group, an ethyl group, or a halogen atom, X ³¹ represents a divalent linking group, and R ³³ represents a single bond, or an alkoxy group. In addition, n _a3 has the same meaning as the general formula (a3-1), including the preferred range.

In the general formula (a3-2), R ³² is a hydrogen atom, a methyl group, an ethyl group, or a halogen atom, more preferably a hydrogen atom or a methyl group, and further preferably a methyl group.

In the general formula (a3-2), examples of the divalent linking group of X ³¹ include -O-, -S-, and -N(R ⁴ )-. Among these, -O- is more preferable.

Here, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group may have a linear structure or a branched structure, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tertiary butyl groups, preferably hydrogen Atom, methyl.

In addition, as the alkyleneoxy group of R ³³ , it is preferably 1 to 4 carbon atoms. The alkoxy group may also have a branched structure. In addition, it may have a substituent or may not be substituted. Examples of the substituent that may be included include halogen atoms. As specific examples of the alkoxy group, a methyleneoxy group, an ethoxy group, a propoxy group, a butoxy group and the like can be exemplified.

Among these, R ^{33 is} preferably an unsubstituted linear alkoxy group having 1 to 4 carbon atoms, or a single bond, more preferably a single bond.

By using the monomer represented by the general formula (a3-2), a polymer having a repeating unit represented by the following general formula (U-a3-1) can be obtained.

With regard to such a polymer, one of the preferred forms has a repeating unit represented by the general formula (U-a3-1).

In the general formula (U-a3-1), n _a3 has the same meaning as the general formula (a3-1) including the preferred range, and R ³² , X ³¹ , and R ³³ are the same as The general formula (a3-2) also includes the same meaning within the preferable range.

The specific example of the monomer represented by general formula (a3-2) is shown below. However, the present invention is not limited to these specific examples.

[Chem 19]

<<Construction unit with photo-alignment group>>

The polymer component A1 contains a polymer including the structural unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton, and an alkyl group having 10 to 30 carbon atoms , And contains constituent units with photo-alignment groups.

Here, the photo-alignment group refers to a photo-reactive group imparted with alignment by photo-dimerization reaction or photo-isomerization reaction.

In addition, examples of the group imparting alignment by the photodimerization reaction include, for example, at least one derivative selected from the group consisting of maleimide derivatives, cinnamic acid derivatives, and coumarin derivatives. Specific examples of the group to be introduced include cinnamate group and chalcone group. In addition, as the cinnamate group and the chalcone group, for example, the following structure can be introduced (in the following formula, * represents a connection site to the polymer chain, and R represents a hydrogen atom or a monovalent organic group), and , * Indicates that the linking site to the polymer chain can be directly bonded to the The main chain of a polymer such as polymer A1-1 may be bonded via a divalent linking group. The monovalent organic group represented by R is preferably an alkyl group or an aryl group. In addition, the carbon number of the monovalent organic group represented by R is preferably 1-10, more preferably 1-7.

On the other hand, as the reactive group isomerized by the action of light, specifically, for example, a group selected from the group consisting of an azobenzene compound, a stilbene compound, and a spiropyran compound can be suitably cited. Groups of skeletons of at least one compound in

Among these, from the viewpoint of the difference between the patterned exposure and the alignment exposure, it is preferable to provide the alignment group by the photodimerization reaction with a shorter-wavelength light reaction, more preferably a cinnamate group or Chalcone. In addition, the pattern exposure here has the same meaning as the exposure step in the manufacturing method of the hardened|cured material of this invention mentioned later, and the "alignment exposure" means that the resin composition is applied on the substrate to impart alignment. The exposure performed has the same meaning as the photo-alignment treatment in the method for manufacturing a cured product of the present invention described later.

The main chain skeleton of the polymer containing the structural unit having a photo-alignment group is not particularly limited, and the molecular design of the side chain is diverse, and the main chain is easily formed by the radical polymerization reaction of the ethylenically unsaturated compound. It is preferably a polymer having a repeating unit represented by the following general formula III.

(In Formula III, R ¹ represents a hydrogen atom or an alkyl group. X represents an aryl group, -(C=O)-O-, or -(C=O)-NR-(R represents a hydrogen atom or carbon number 1 1-4 alkyl groups). L represents a single bond or a divalent linking group, and P represents a photo-alignment group.)

Here, in Formula III, R ¹ represents a hydrogen atom or an alkyl group, and the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl) Base etc.). R ^{1 is} preferably a hydrogen atom or a methyl group.

In general formula III, L represents a single bond or a divalent linking group. As the divalent linking group, -O-, -S-, alkylene group, arylene group, or a combination of these Groups. The alkylene group represented by L may have a linear, branched, or cyclic structure, and a linear structure is preferred. The carbon number of the alkylene group represented by L is preferably from 1 to 10, more preferably from 1 to 6, and even more preferably from 2 to 4. In addition, examples of the arylene group represented by L include phenylene group, tolyl group, and xylylene group, and preferably phenylene group.

In the general formula III, P represents a photo-alignment group, and as specific examples thereof, a chalcone group, a cinnamate group, a distyryl group, a maleimide group, and an azobenzyl group can be suitably mentioned. Among them, chalcone group and cinnamate group are more preferable. In addition, the optical alignment group represented by P may have a substituent as long as it does not lose optical alignment. Specific substituents include, for example, halo, alkyl, aryl, etc., preferably alkyl or aryl. The carbon number of the alkyl group or aryl group is preferably 1-10, more preferably 1-7.

Preferred specific examples of polymers having a repeating unit represented by general formula III are shown below, but the present invention is not limited to these specific examples.

[化22]

[化23]

[化24]

[化25]

[化26]

[化27]

[Chem 28]

The polymer having the repeating unit represented by the general formula III can be synthesized by (a) polymerizing the corresponding monomer and directly introducing a photoreactive group, or by (b) reacting the light by a polymer reaction It is synthesized by introducing a sexual group into a polymer obtained by polymerizing a monomer having an arbitrary functional group. In addition, the methods (a) and (b) may be combined for synthesis.

Here, examples of the polymerization reaction that can be used in the methods (a) and (b) include radical polymerization, cationic polymerization, and anionic polymerization.

In addition, the polymer having a repeating unit represented by general formula III may also be A copolymer containing a plurality of repeating units represented by the general formula III may also be a copolymer containing a repeating unit other than the general formula III (for example, a repeating unit not containing an ethylenically unsaturated group).

(Better form of constituent unit s1)

With respect to the constituent units of all polymer components, the constituent unit s1 is preferably 0.01 mol% to 10 mol%, more preferably 0.1 mol% to 5 mol%, and further preferably 0.1 mol% to 3 Molar %, especially good is 0.1 mol% ~ 2 mol%, the best is 0.5 mol% ~ 2 mol%.

When the polymer having the structural unit s1 has the structural unit a1 and the structural unit a2, the content of the structural unit s1 is preferably 20 mol% to 90 mol% relative to all the structural units of the polymer It is more preferably 20 mol% to 80 mol%, and further preferably 20 mol% to 70 mol%.

In the case where the polymer having the structural unit s1 has only one of the structural unit a1 and the structural unit a2, the content of the structural unit s1 is preferably 30 mol% relative to all the structural units of the polymer ~90 mol%, more preferably 30 mol% to 80 mol%, and further preferably 30 mol% to 70 mol%.

When the polymer having the structural unit s1 does not have any one of the structural unit a1 and the structural unit a2, the content of the structural unit s1 is preferably 40 mol% relative to all the structural units of the polymer ~95 mol%, more preferably 40 mol% to 90 mol%, and further preferably 40 mol% to 80 mol%.

<Other components>

In the first aspect, the polymer component A1 is formed in addition to the constituent unit a1 In addition to the unit a2 and the structural unit s1, a polymer including a structural unit a3 having an acid group or a structural unit a4 other than these may be contained.

<<Construction unit a3>>

The polymer component A1 preferably contains the following polymer for the reason that it is not only easily dissolved in an alkaline developer and has good developability, but also excellent sensitivity, and also excellent fine-line adhesion of the cured product after development. The polymer contains a structural unit a3 having an acid group.

The acid group in the present invention refers to a proton dissociative group with a pKa of less than 11. Regarding the acid group, a monomer that can form an acid group is generally used, and is incorporated into the polymer in the form of a constituent unit containing the acid group. By including a structural unit containing such an acid group in a polymer, there is a tendency to easily dissolve in an alkaline developer.

Examples of the acid group used in the present invention include carboxylic acid group, sulfonamide group, phosphonic acid group, sulfonic acid group, phenolic hydroxyl group, sulfonyl amide imine group, and acid anhydride groups of these acid groups, A group having a salt structure by neutralizing these acid groups is preferably a carboxylic acid group and/or a phenolic hydroxyl group. The salt is not particularly limited, and alkali metal salts, alkaline earth metal salts, and organic ammonium salts can be preferably exemplified.

The structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, or a structural unit derived from (meth)acrylic acid and/or its ester. For example, the compounds described in Paragraph 0021 to Paragraph 0023 and Paragraph 0029 to Paragraph 0044 of Japanese Patent Laid-Open No. 2012-88459 can be used, and this content is incorporated into the specification of the present application. Among them, the structural units derived from p-hydroxystyrene, (meth)acrylic acid, maleic acid, and maleic anhydride are preferred.

The structural unit a3 having an acid group is preferably a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group from the viewpoint of sensitivity, and more preferably a structural unit having a carboxyl group.

Specific examples of the structural unit a3 having an acid group include a structural unit a1-1-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, and a structure having both an ethylenic unsaturated group and an acid anhydride. The constitutional unit a1-1-2 and the constitutional unit a1-2-1 having a phenolic hydroxyl group are also preferably the same.

Among them, the structural unit a3 having an acid group is preferably a structural unit derived from a compound selected from the group consisting of methacrylic acid, acrylic acid, and p-hydroxystyrene (Formula a3-1 to Formula a3- The structural unit represented by any of 3) is more preferably a structural unit derived from methacrylic acid (a structural unit represented by the following formula a3-1) or a structural unit derived from acrylic acid (the following formula a3-2 The represented structural unit) is more preferably a structural unit derived from methacrylic acid (a structural unit represented by the following formula a3-1).

(Preferable form of constituent unit a3)

The structural unit a3 containing an acid group is preferably 1 mol% to 80 mol%, more preferably 1 mol% to 50 mol%, and further preferably 5 mol% relative to the structural units of all polymer components ~40 mol%, especially good is 5 mol%~30 mol%, the best is 5 mol%~20 mol%.

When the polymer having the structural unit a3 has the structural unit a1 and the structural unit a2, the content of the structural unit a3 is preferably 1 mol% to 30 mol% relative to all the structural units of the polymer It is more preferably 3 mol% to 20 mol%, and further preferably 5 mol% to 15 mol%.

When the polymer having the structural unit a3 has only one of the structural unit a1 and the structural unit a2, the content of the structural unit a3 is preferably 1 mol% relative to all the structural units of the polymer ~50 mol%, more preferably 5 mol% to 45 mol%, and further preferably 10 mol% to 40 mol%.

When the polymer having the structural unit a3 does not have any one of the structural unit a1 and the structural unit a2, the content of the structural unit a3 is preferably 1 mol% relative to all the structural units of the polymer ~50 mol%, more preferably 2 mol% to 40 mol%, and further preferably 3 mol% to 30 mol%.

<<Construction unit a4>>

The monomers constituting the structural unit a4 other than the structural unit a1, the structural unit a2, the structural unit s1, and the structural unit a3 are not particularly limited, and examples thereof include styrenes, alkyl (meth)acrylates, Cyclic alkyl (meth)acrylate, aryl (meth)acrylate, unsaturated dicarboxylic acid diester, bicyclic unsaturated compounds, Maleimide compounds, unsaturated aromatic compounds.

The monomers forming the other constituent unit a4 may be used alone or in combination of two or more.

Other structural units a4 specifically include styrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, vinylbenzoic acid Methyl ester, ethyl vinyl benzoate, 4-hydroxybenzoic acid (3-methacryloxypropyl) ester, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic acid N-propyl ester, isopropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate Structural units derived from esters, acrylonitrile, ethylene glycol mono(meth)acrylate, etc. In addition, the compounds described in paragraphs 0021 to 0024 of Japanese Patent Laid-Open No. 2004-264623 can be cited.

In addition, the other structural unit a4 is preferably a structural unit derived from styrene or a monomer having an aliphatic cyclic skeleton from the viewpoint of electrical characteristics. Specific examples include styrene, methylstyrene, α-methylstyrene, dicyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, (methyl ) Benzyl acrylate, etc.

Furthermore, the other structural unit a4 is preferably a structural unit derived from an alkyl (meth)acrylate from the viewpoint of adhesion. Specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and more preferably methyl (meth)acrylate. Of all the structural units constituting the polymer, the content of the structural unit a4 is preferably 60 mol% or less, more preferably 50 mol% or less, and more preferably 40 mol% or less. The lower limit may be 0 mol%, but for example, it is preferably 1 mol% or more, and more preferably 5 mol% or more. Within the range of the above-mentioned numerical values, the properties of the cured film obtained from the resin composition are good.

<Combination of polymers>

As long as the polymer having the structural unit a1, the structural unit a2 and the structural unit s1, the structural unit a3 and the structural unit a4 satisfies the above conditions 1 to 5, the combination of structural units or the number of polymers is not Specially limited. In addition, in the case where the conditions 1 to 3 described above do not include the crosslinking agent C1 described below, it is necessary to polymerize the structural unit a1 including at least an acid group protected by an acid decomposable group The substance A1-1 further contains a structural unit a2 having a crosslinkable group; or must contain another polymer A1-2, which contains a structural unit a2 having a crosslinkable group.

Therefore, as the polymer component A1, for example, it may be in a state that it contains only the polymer A1-1 containing the structural unit a1 having a group protected by an acid-decomposable group, and This polymer A1-1 is a polymer including all of the structural unit a2 having a crosslinkable group, the structural unit s1, and the structural unit a3 having an acid group.

In addition, as the polymer component A1, it may be in a form that contains a polymer A1-1 and contains another polymer A1-2, and the polymer A1-1 contains an acid group protected by an acid-decomposable group A structural unit a1 of the group, the polymer A1-2 contains a structural unit a2 having a crosslinkable group, and the polymer A1-2 contains a structural unit s1, and a polymer having a structural unit a3 having an acid group.

In addition, as the polymer component A1, it may be in the form of containing a polymer A1-1, another polymer A1-2, and another polymer A1-3 containing a structural unit s1, the polymer A1- 1 includes a structural unit a1 having a group having an acid group protected by an acid-decomposable group, and the polymer A1-2 includes a structural unit a2 having a crosslinkable group.

In addition, when the resin composition contains the crosslinking agent C1 described later, the polymer component A1 may also be in the form of containing the polymer A1-1 and another polymer A1-3 containing the constituent unit s1, The polymer A1-1 includes a structural unit a1 having a group in which an acid group is protected by an acid-decomposable group.

In the first aspect of the present invention, the polymer component A1 may include the polymer having only the structural unit a3 and the structural unit a4.

As such a polymer, a resin having a carboxyl group in the side chain is preferred. For example, Japanese Patent Publication No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Publication No. 59-53836 No., Japanese Patent Laid-Open No. 59-71048 as described in the methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified horse Leucic acid copolymers and the like, acidic cellulose derivatives having a carboxyl group on the side chain, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, etc. Furthermore, it may be cited that the side chain has a (meth)acryloyl group As the preferred polymer. The term "substantially not included" means that the weight ratio in the polymer is 1% by mass or less.

For example, benzyl (meth)acrylate/(meth)acrylic acid copolymer, 2-hydroxyethyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, 2-hydroxypropyl (meth)acrylate described in Japanese Patent Laid-Open No. 7-140654/ Polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/ Methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer Body/benzyl methacrylate/methacrylic acid copolymer, etc.

In addition, Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-140144, Japanese Patent Laid-Open No. 11 -174224, Japanese Patent Laid-Open No. 2000-56118, Japanese Patent Laid-Open No. 2003-233179, Japanese Patent Laid-Open No. 2009-52020, etc., known polymer compounds, which are incorporated To the specification of this application.

These polymers may contain only one kind or two or more kinds.

As these polymers, commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above are made by Sartomer), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (the above is manufactured by East Asia Synthetic Co., Ltd.), Tsukatake (JONCRYL) 690, Tsukatake (JONCRYL) 678, Tsukamura JONCRYL 67, JONCRYL 586 (above manufactured by BASF), etc.

<molecular weight>

The molecular weight of the polymer in the polymer component A1 in terms of polystyrene-equivalent weight average molecular weight is preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and still more preferably 10,000 to 20,000. If it is within the range of the above-mentioned numerical values, the characteristics are good. The ratio of the number average molecular weight Mn to the weight average molecular weight Mw (degree of dispersion, Mw/Mn) is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.

In addition, the measurement of the weight average molecular weight or the number average molecular weight in the present invention is preferably performed by a gel permeation chromatography (Gel Permeation Chromatography, GPC) method. Regarding the measurement by the gel permeation chromatography method in the present invention, it is preferable to use HLC-8020GPC (manufactured by Tosoh), and use TSKgel Super HZ MH, TSKgel Super HZ4000, TSKgel Super HZ200 (East Manufactured by Tosoh Co., Ltd. (4.6 mmID×15 cm) as a column, THF (tetrahydrofuran) was used as the eluent.

<Preparation method>

Various methods are known for the synthesis method of the polymer in the polymer component A1. To give an example, a radical polymerization polymerizable unit amount for forming each of the constituent units can be included by using a radical polymerization initiator The monomeric radical polymerizable monomer mixture is synthesized by polymerization in an organic solvent. In addition, it can also be synthesized by a so-called polymer reaction.

<content>

In the first aspect of the present invention, the content of the polymer component A1 relative to the total solid content of the resin composition is preferably 20% by mass to 95% by mass, more preferably 50% by mass to 95% by mass, and further preferably It is 55% to 95% by mass. If the content is within this range, an organic film with good curability can be obtained.

In addition, in the first aspect of the present invention, the content of the polymer having the constituent unit s1 relative to the total solid content of the resin composition is preferably 0.1% by mass to 20% by mass, more preferably 0.1% by mass to 10 quality%.

[Photoacid generator B1]

The first aspect of the present invention contains a photoacid generator B1.

The photoacid generator B1 is preferably a compound that generates an acid by sensing actinic rays with a wavelength of 300 nm or more, preferably with a wavelength of 300 nm to 450 nm, and its chemical structure is not limited. In addition, a photoacid generator that does not directly induce actinic rays with a wavelength of 300 nm or more can be combined with a sensitizer as long as it is a compound that induces actinic rays with a wavelength of 300 nm or more and generates an acid by using it together with the sensitizer. It is preferably used. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid with a pKa of 4 or less, more preferably a photoacid generator that generates an acid with a pKa of 3 or less, and most preferably a pKa of Photoacid generator with 2 or less acids. Furthermore, in the present invention, pKa basically refers to pKa in water at 25°C. The pKa that cannot be measured in water is obtained by changing to a solvent suitable for the measurement and performing the measurement. Specifically, the pKa described in the chemical handbook or the like can be used as a reference. The acid having a pKa of 3 or less is preferably sulfonic acid or phosphonic acid, and more preferably sulfonic acid.

Examples of the photoacid generator B1 include onium salt compounds, tris Chloromethyl s-triazines, osmium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, amide imine sulfonate compounds, oxime sulfonate compounds, etc. Among these, onium salt compounds, amide imine sulfonate compounds, and oxime sulfonate compounds are preferred, and onium salt compounds and oxime sulfonate compounds are particularly preferred. The photoacid generator may be used alone or in combination of two or more.

As specific examples of trichloromethyl s-triazines, diarylionium salts, triarylammonium salts, quaternary ammonium salts, and diazomethane compounds, Japanese Patent Laid-Open No. 2011-221494 can be exemplified The compounds described in paragraph No. 0083 to paragraph No. 0088 or the compounds described in Paragraph No. 0013 to Paragraph No. 0049 of Japanese Patent Laid-Open No. 2011-105645 are incorporated into the specification of the present application.

As a specific example of the amide imine sulfonate compound, the compounds described in paragraph No. 0065 to paragraph No. 0075 of WO2011/087011 can be exemplified, and these contents are incorporated into the specification of the present application.

As the onium salt, preferably diaryl iodonium salts or triaryl alkoxide salts are exemplified.

Examples of the diaryl iodide salts are preferably diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethanesulfonate, and 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate. 、4-Methoxyphenyl phenyl phosphonium trifluoroacetate, phenyl, 4-(2'-hydroxy-1'-tetradecyloxy) phenyl chloro-trifluoromethanesulfonate, 4-(2 '-Hydroxy-1'-tetradecyloxy) phenyl antimonium hexafluoroantimonate, phenyl, 4-(2'-hydroxy-1'-tetradecyloxy) phenyl antimony-p-toluenesulfonic acid salt.

As triaryl alkane salts, preferably, triphenyl alkane trifluoromethanesulfonate, Triphenylammonium trifluoroacetate, 4-methoxyphenyldiphenylammonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylammonium trifluoroacetate, 4-phenylphenylthio Diphenylammonium trifluoromethanesulfonate, or 4-phenylphenylthiodiphenylammonium trifluoroacetate.

As the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure, a compound containing an oxime sulfonate structure represented by the following general formula (B1-1) can be preferably exemplified.

General formula (B1-1)

In the general formula (B1-1), R ²¹ represents an alkyl group or an aryl group. The wavy line represents bonds with other groups.

In the general formula (B1-1), any group may be substituted, and the alkyl group of R ²¹ may be linear or branched or cyclic. The allowable substituents are explained below.

The alkyl group of R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ²¹ may be a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cyclic alkyl group (including 7,7-dimethyl-2-oxo Bridged alicyclic groups such as norbornyl, preferably bicycloalkyl, etc.) are substituted.

The aryl group of R ²¹ is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group of R ²¹ may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

The compound containing the oxime sulfonate structure represented by the general formula (B1-1) is also preferably the oxime sulfonate compound described in paragraphs 0108 to 0133 of Japanese Patent Laid-Open No. 2014-238438.

The amide imine sulfonate-based compound is preferably a naphthalene amide imide-based compound, which can be referred to the description in International Publication WO11/087011, and these contents are incorporated in the specification of the present application. In the present invention, particularly preferably, trifluoromethylsulfonyloxybicyclo[2.2.1]hept-5-enedicarboxylimide, succinimide trifluoromethanesulfonate, ortho Xylylenediimide trifluoromethanesulfonate, N-hydroxynaphthalene dimethylimide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyamideimine propanesulfonic acid ester.

In the first aspect of the present invention, the content of the photoacid generator B1 is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the total solid content of the resin composition. For example, the lower limit is more preferably 0.2 parts by mass or more, and further preferably 0.5 parts by mass or more. The upper limit is, for example, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less.

[Crosslinking agent C1]

The first aspect of the present invention contains a crosslinking agent C1 having a molecular weight of 1,000 or less when the condition 1 and the condition 2 are not satisfied, that is, when the polymer component A1 does not contain a polymer having a crosslinkable group. In addition, even when the above condition 1 or condition 2 is satisfied, the crosslinking agent C1 may be contained.

The crosslinking agent C1 can be used without limitation as long as it causes a crosslinking reaction by heat.

For example, it is preferably selected from compounds having two or more epoxy groups or oxetanyl groups, blocked isocyanate compounds (having protected Isocyanate group compound), an alkoxymethyl group-containing compound, or a compound consisting of a compound having at least one ethylenically unsaturated double bond (ethylenically unsaturated group), more preferably at least one selected from the group consisting of molecules At least one of the group consisting of a compound having two or more epoxy groups or oxetanyl groups, and a blocked isocyanate compound.

The addition amount of the cross-linking agent C1 is preferably 0 to 30 parts by mass, more preferably 1 to 20 parts by mass relative to 100 parts by mass of the total solid content of the resin composition. In addition, a plurality of crosslinking agents may be used in combination. In this case, the addition amount is calculated based on the total content obtained by adding up all the crosslinking agents.

Hereinafter, the crosslinking agent C1 which can be preferably used in the present invention will be described.

<A compound having two or more epoxy groups or oxetanyl groups in the molecule>

As the crosslinking agent C1, for example, a multifunctional small ring cyclic ether compound can be mentioned.

That is, it means a compound having two or more epoxy groups and/or oxetanyl groups in one molecule.

Specific examples of compounds having two or more epoxy groups in the molecule include aliphatic epoxy compounds.

These are available as commercial products. Examples include: Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-614B, Dena Denacol EX-622, Denacol EX-512, Denacol EX-521, Denacol EX-411, Denacol EX-411 -421, Denakau Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-211, Denacol EX-211 212, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol (Denacol) EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-911 , Denacol EX-941, Denacol EX-920, Denacol EX-931, Denacol EX-212L, Denacol ( Denacol) EX-214L, Denacol EX-216L, Denacol EX-321L, Denacol EX-850L, Denacol DLC-201 Denacol DLC-203, Denacol DLC-204, Denacol DLC-205, Denacol DLC-206, Denacol ) DLC-301, Denacol DLC-402 (above are manufactured by Nagase ChemteX), Celloxide 2021P, Celloxide 2081, Sai Celloxide 3000, Celloxide EHPE3150, EPOLEAD GT400, Serubinasu B0134, Serubinasu B0177 (Daicel) ) Manufacturing) etc.

These can be used alone or in combination of two or more.

As a specific example of a compound having two or more oxetanyl groups in the molecule, Aron Oxetane (Aron Oxetane) OXT-121, Alon Oxygen Aron Oxetane OXT-221, Aron Oxetane OX-SQ, Aron Oxetane PNOX (above manufactured by East Asia Synthetic Co., Ltd.).

In addition, the oxetanyl group-containing compound is preferably used alone or in combination with an epoxy group-containing compound.

<Blocked isocyanate compound>

As the crosslinking agent C1, a blocked isocyanate-based compound can also be preferably used.

The blocking isocyanate compound is not particularly limited as long as it has a chemically protected isocyanate group-blocking isocyanate group compound, and from the viewpoint of curability, it is preferably a compound having two or more blocking isocyanate group per molecule.

In addition, the term “isocyanate group blocking” in the present invention refers to a group that can generate an isocyanate group by heat. For example, a group that reacts a blocking agent with an isocyanate group to protect the isocyanate group is preferably exemplified. In addition, the blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90°C to 250°C.

In addition, the skeleton of the blocked isocyanate compound is not particularly limited, as long as it has two isocyanate groups in one molecule, it may be any compound, and may be an aliphatic, alicyclic, or aromatic polyisocyanate, for example, it may be suitably Use 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetra Methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1 , 10-decylmethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'-diethyl ether diisocyanate, diphenyl methyl Alkane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene Diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, terephthalic diisocyanate, 3,3'-methylene xylene-4,4'-diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorobenzene diisocyanate, norbornane diisocyanate, hydrogenated 1,3-xylene diisocyanate, hydrogenated 1,4-xylene diisocyanate and other isocyanate compounds Compound-derived prepolymer-type skeleton compounds. Among these, particularly preferred are tolylene diisocyanate (TDI) or diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (TDI) isophorone diisocyanate (IPDI).

Examples of the parent structure of the blocked isocyanate compound used in the curable composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.

Examples of the blocking agent that forms the blocking structure of the blocking isocyanate compound include oxime compounds, amide compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, thiol compounds, and imidazole compounds. Compounds, amide imide compounds, etc. Among these, particularly preferred is a blocking agent selected from the group consisting of oxime compounds, amide compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds.

Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, and methyl. Ethyl ketoxime, cyclohexanone oxime, benzophenone oxime, etc.

Examples of the lactam compound include ε-caprolactam, γ-butyramamide, and the like.

Examples of the phenol compound include phenol, naphthol, cresol, xylenol, halogen-substituted phenol, and the like.

Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.

Examples of the amine compound include primary amines and secondary amines, which may be any of aromatic amines, aliphatic amines, and alicyclic amines, and examples include aniline, diphenylamine, ethyleneimine, and polyamine. Ethylene imine, etc.

Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, and methyl acetoacetate. Examples of the pyrazole compound include pyrazole, methylpyrazole, and dimethylpyrazole.

Examples of the thiol compound include alkyl mercaptan and aryl mercaptan.

The blocked isocyanate compound that can be used in the curable composition of the present invention can be obtained as a commercially available product. For example, Coronate AP stable M and Coronate can be preferably used. )2503, Coronate 2515, Coronate 2507, Coronate 2513, Coronate 2555, Millionate MS-50 (the above are Japan Polyurethane Industry Co., Ltd.), Takenate B-830, Takenate B-815N, Takenate B-820NSU, Takenate B -842N, Takenate B-846N, Takenate B-870N, Takenate B-874N, Takenate B-882N (above manufactured by Mitsui Chemicals Co., Ltd.), Duranate 17B-60PX, Duranate 17B-60P, Duranai Duranate TPA-B80X, Duranate TPA-B80E, Duranate MF-B60X, Duranate MF-B60B, Duranate MF-B60B, Duranate MF- K60X, Duranate MF-K60B, Duranate E402-B80B, Duranate SBN-70D, Duranate SBB-70P, Duranate (Duranate) K6000 (made by Asahi Kasei Chemicals Co., Ltd.), Desmodule BL1100, Desmodule BL1265 MPA/X, Desmodule BL3575/1, Desmodule BL3272MPA, Desmodule BL3370MPA, Desmodule BL3475BA/SN, Desmodule BL5375MPA, Desmodule VPLS2078/2, Desmodule BL4265SN, Desmol ( Desmodule) PL340, Desmodule (PLs) PL350, Sumidule (Sumidule) BL3175 (above manufactured by Suwa Bayer Amine Co., Ltd.), etc.

<Crosslinking agent containing alkoxymethyl group>

As the alkoxymethyl group-containing compound, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like are preferred. These are obtained by converting the methylol groups of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylolated urea into alkoxymethyl groups, respectively. The type of the alkoxymethyl group is not particularly limited, and examples include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, etc. From the viewpoint of the amount of generated, particularly preferred is methoxymethyl.

Among these compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are preferred compounds. From the viewpoint of transparency, particularly preferred It is an alkoxymethylated glycoluril.

Regarding the alkoxymethyl group-containing crosslinking agent, a compound having a molecular weight of 1,000 or less is also used for the curable composition.

These alkoxymethyl-containing compounds can be obtained as commercially available products, for example, Semel (CYMEL) 300, Semel (CYMEL) 301, Semel (CYMEL) 303, Semel can be preferably used. (CYMEL) 370, Semel (CYMEL) 325, Semel (CYMEL) 327, Semel (CYMEL) 701, Semel (CYMEL) 266, Semel (CYMEL) 267, Semel ( CYMEL) 238, Semel (CYMEL) 1141, Semel (CYMEL) 272, Semel (CYMEL) 202, Semel (CYMEL) 1156, Semel (CYMEL) 1158, Semel (CYMEL) 1123, Semel (CYMEL) 1170, Semel (CYMEL) 1174, Semel (CYMEL) UFR65, Semel (CYMEL) 300 (above manufactured by Mitsui Cyanamid), Niccarak ( Nikalac MX-750, Nikalac MX-032, Nikalac MX-706, Nikalac MX-708, Nikalac MX-40, Nikalak (Nikarac) Nikalac) MX-31, Nikalac MX-270, Nikalac MX-280, Nikalac MX-290, Nikalac MS-11, Nikalak (Niklac) Nikalac) MW-30HM, Nikalac MW-100LM, Nikalac MW-390 (above manufactured by Sanwa Chemical Co., Ltd.), etc.

[Second aspect of the invention]

The second aspect of the present invention contains the following polymer component A2 and quinonediazide compound B2.

[Polymer component A2]

The polymer component A2 contained in the second aspect of the present invention is a polymer component containing a polymer A2-1 containing the structural unit a3 having an acid group.

In addition, the polymer component A2 refers to those that include other polymers added as needed in addition to the polymer A2-1.

In addition, the polymer contained in the polymer component A2 is the same as the polymer contained in the polymer component A1 of the first aspect, and is preferably an addition polymerization type polymer, and more preferably contains a polymer derived from (methyl ) A polymer of acrylic acid and/or its ester constituting the unit.

The second aspect of the present invention must satisfy at least one of the conditions shown in the following 1 to 3, and must satisfy at least one of the conditions shown in the following 4 and 5.

This means that the polymer A2-1 containing the structural unit a3 having an acid group is separate from the polymer A2-1 and must have a crosslinkable group portion or component that contributes to hardening; The constituent unit of the alignment group and the polymer component that biases the constituent unit existing on the surface.

Therefore, in the following description, the structural units in the polymer necessary as a polymer component are mainly described, not for each polymer.

(condition)

1: The polymer A2-1 further includes a structural unit a2 having a crosslinkable group

2: The polymer component A2 further contains a polymer A2-2, and the polymer A2-2 includes a structural unit a2 having a crosslinkable group

3: It further contains a crosslinking agent C2 having a crosslinking group and a molecular weight of 1,000 or less

4: The polymer A2-1 or the polymer A2-2 contains the structural unit represented by the following s1

5: The polymer component A2 further contains a polymer A2-3 containing a structural unit represented by the following s1

s1: a structural unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton, and a C10-30 alkyl group, and a structural unit having a photo-alignment group

<Construction unit a3>

The polymer component A2 includes a polymer A2-1 including at least a structural unit a3 having an acid group.

Here, the structural unit a3 having an acid group has the same meaning as the structural unit a3 having an acid group in the polymer component A1 of the first aspect, and the preferred ranges are also the same.

In the second aspect, it is preferable to contain the structural unit a3 of 3 mol% to 70 mol% in all the structural units of the polymer, more preferably contain 5 mol% to 60 mol %, and further preferably Contains 10 mol% to 50 mol% By setting the use ratio of the structural unit a3 to the above range, the solubility is optimized, and a resin composition excellent in sensitivity can be obtained.

<Construction unit a2>

The polymer component A2 preferably contains a polymer containing A structural unit a2 having a crosslinkable group. In addition, in the case where the conditions 1 to 3 described above do not include the crosslinking agent C2 described later, the polymer A2-1 including at least the structural unit a3 having an acid group must further include crosslinking. The structural unit a2 of the sexual group; or must contain another polymer A2-2, which contains the structural unit a2 having a crosslinkable group.

Here, the structural unit a2 having a crosslinkable group has the same meaning as the structural unit a2 having a crosslinkable group in the polymer component A1 of the first aspect, and the preferred range is also the same.

In the second aspect, it is preferable to contain the structural unit a2 of 0 mol% to 70 mol% in all the structural units of the polymer, and more preferably to contain 0 mol% to 50 mol%. By setting the use ratio of the structural unit a2 to the above range, a cured film having excellent characteristics can be formed. In addition, as described above, when the content of the constituent unit a2 is 0 mol %, it is necessary to contain the crosslinking agent C2 described later.

<Construction unit shown in s1>

The polymer component A2 contains a polymer including the structural unit s1 represented by the following s1. Furthermore, as shown in the above conditions 4 and 5, the structural unit s1 may be (A) the polymer A2-1 including at least the structural unit a3 having an acid group, and the form of the structural unit s1; (B) The other polymer A2-2 including the structural unit a2 having a crosslinkable group further has the aspect of the structural unit s1; and (C) the other polymer A2-3 has any of the aspect of the structural unit s1.

s1: a structural unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton, and an alkyl group having 10 to 30 carbon atoms, and having light Constituent unit

Here, the structural unit s1 has the same meaning as the structural unit s1 in the polymer component A1 of the first aspect, and the preferred ranges are also the same.

In the second aspect of the present invention, as in the first aspect, the content of the polymer having the constituent unit s1 relative to the total solid content of the resin composition is preferably 0.1% by mass to 20% by mass, more preferably It is 0.1% by mass to 10% by mass.

<Other components>

In the second aspect, the polymer component A2 may contain a polymer having a structural unit a5 other than these, in addition to the structural unit a3, the structural unit a2, and the structural unit s1.

The monomer that becomes the structural unit a5 is not particularly limited as long as it is an unsaturated compound other than the structural unit a3 and the structural unit a2.

Specific examples of the radically polymerizable monomer used to form the structural unit a5 include, for example, chain alkyl methacrylate, cyclic alkyl methacrylate, chain alkyl acrylate, and acrylic ring. Alkyl ester, aryl methacrylate, aryl acrylate, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, including tetrahydrofuran An unsaturated compound of a skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, a skeleton represented by the following formula (4), other unsaturated compounds, and the like. As a specific example of the radically polymerizable singular body used to form the constituent unit a5, the compounds described in paragraph No. 0046 to paragraph No. 0065 of Japanese Patent Laid-Open No. 2012-88459 can be used, and the contents are incorporated into this document In the application specification.

In the formula (4), R ²³ is a hydrogen atom or a methyl group. s is an integer of 1 or more.

Among these structural units a5, preferably chain alkyl methacrylate, cyclic alkyl methacrylate, maleimide compound, having tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran The skeleton, the unsaturated compound of the skeleton represented by the formula (4), the unsaturated aromatic compound, the cyclic alkyl acrylate, and acryloylmorpholine. Among these, in terms of copolymerization reactivity and solubility in an alkaline aqueous solution, styrene, methyl methacrylate, third butyl methacrylate, n-lauryl methacrylate, Tricyclomethacrylate [5.2.1.0 ^2,6 ]decane-8-yl, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexyl Maleimide, tetrahydrofurfuryl (meth)acrylate, polyethylene glycol (n=2~10) mono(meth)acrylate, 3-(meth)acryloyltetrahydrofuran-2-one , Acryloyl Morpholine. These compounds may be used alone or in combination of two or more.

In the second aspect, it is preferable to contain the structural unit a5 of 1 mol% to 90 mol% in all the structural units of the polymer, more preferably to contain 5 mol% to 80 mol %, and further preferably Contains 7 mol% to 60 mol%. By using the component a5 By setting the ratio within the above range, a cured film having excellent characteristics can be formed.

[Quinonediazide compound B2]

The second aspect of the present invention contains a quinonediazide compound B2.

As the quinonediazide compound B2, a 1,2-quinonediazide compound that generates a carboxylic acid by irradiation with actinic rays can be used.

As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as "master core") and 1,2-naphthoquinonediazide sulfonyl halide can be used. As specific examples of these compounds, for example, reference can be made to the descriptions in paragraph No. 0075 to paragraph No. 0078 of Japanese Patent Laid-Open No. 2012-088459, and the contents are incorporated into the specification of the present application.

In the condensation reaction of a phenolic compound or an alcoholic compound (master core) with 1,2-naphthoquinone diazide sulfonyl halide, it is preferable to use the number of OH groups in the phenolic compound or alcoholic compound. The 1,2-naphthoquinonediazide sulfonamide is 30 mol% to 85 mol%, more preferably 50 mol% to 70 mol%. The condensation reaction can be carried out by a known method.

In addition, as the 1,2-quinonediazide compound, 1,2-naphthoquinonediazidesulfonamides in which the ester bond of the exemplified parent core is changed to an amide bond can also be suitably used, for example, 2 , 3,4-triaminobenzophenone-1,2-naphthoquinonediazide-4-sulfonamide, etc. In addition, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol (1.0 mol) and 1 , 2-naphthoquinonediazide-5-sulfonyl chloride (3.0 mol) condensate, 1,1,1-tris(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinone Condensate of diazide-5-sulfonyl chloride (2.0 mol), 2,3,4,4'-tetrahydroxybenzophenone (1.0 mol) and 1,2- Condensate of naphthoquinonediazide-5-sulfonate (2.44 mol), etc.

These quinonediazide compounds B2 can be used alone or in combination of two or more.

The content of the quinonediazide compound B2 in the second aspect is preferably 1 part by mass to 50 parts by mass, more preferably 2 parts by mass to 40 parts by mass relative to 100 parts by mass of the total solid content in the resin composition. Furthermore, it is preferably 10 to 25 parts by mass.

By setting the formulation amount of the quinonediazide compound B2 to the above range, the difference between the irradiated part of the actinic ray and the unirradiated part in the alkaline aqueous solution that becomes the developer is large, and the patterning performance is good, and the resulting The cured film has good solvent resistance.

[Crosslinking agent C2]

The second aspect of the present invention contains a cross-linking agent C2 with a molecular weight of 1,000 or less when the condition 1 and the condition 2 are not satisfied, that is, when the polymer component A2 does not contain a polymer having a crosslinkable group. In addition, even when the condition 1 or the condition 2 is satisfied, the crosslinking agent C2 may be contained.

Here, the crosslinking agent C2 has the same meaning as the crosslinking agent C1 used in the first aspect, and the preferred range is also the same.

[Organic Solvent D]

The photosensitive resin composition of the first aspect and the second aspect of the present invention (hereinafter also collectively referred to as the “resin composition of the present invention”) preferably contains an organic solvent D.

As the organic solvent D, a known organic solvent can be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, and propylene. Glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl Base ethers, butanediol diacetates, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, alcohols, esters, ketones, amides, lactones, etc. As specific examples of these organic solvents, reference can be made to paragraph 062 of Japanese Patent Laid-Open No. 2009-098616.

Preferred specific examples include: propylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, 1,3-butanediol di Acetate, methoxypropyl acetate, cyclohexanol acetate, propylene glycol diacetate, tetrahydrofurfuryl alcohol.

From the viewpoint of coatability, the boiling point of the organic solvent D is preferably 100°C to 300°C, and more preferably 120°C to 250°C.

The organic solvent D that can be used in the present invention may be used alone or in combination of two or more. It is also preferable to use solvents having different boiling points together.

From the viewpoint of adjusting the viscosity suitable for coating, the content when the organic solvent D is contained relative to 100 parts by mass of the total solid content of the resin composition is preferably 100 parts by mass to 3,000 parts by mass, more preferably 200 parts by mass to 2,000 parts by mass, and more preferably 250 parts by mass to 1,000 parts by mass.

The solid content concentration of the resin composition is preferably 3% by mass to 50% by mass, and more preferably 20% by mass to 40% by mass.

[Sensitizer]

The resin composition of the present invention, particularly the photosensitive tree of the first aspect of the present invention In order to promote decomposition of the fat composition in combination with the photoacid generator B1, it is preferable to contain a sensitizer.

The sensitizer absorbs actinic rays or radiation and becomes an electronically excited state. The sensitizer in an electron-excited state comes into contact with the photoacid generator to produce effects such as electron movement, energy movement, and heat generation. With this, the photoacid generator chemically decomposes and decomposes to generate acid. As an example of a preferable sensitizer, a compound belonging to the following compounds and having an absorption wavelength at any place in the wavelength range of 350 nm to 450 nm can be mentioned.

Polynuclear aromatics (e.g. pyrene, north, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10- Dipropoxyanthracene), xanthenes (e.g. fluorescein, eosin, erythrophyllin, rhodamine B, rose Bengal), xanthones (e.g. xanthones, thioxanthones) , Dimethyl thioxanthone, diethyl thioxanthone), cyanine (such as thiocarbocyanine, oxacarbocyanine), partial cyanine (such as partial cyanine, carbonyl cyanine) ), rhodacyanines, oxazines, thiazines (e.g. thionine, methylene blue, toluidine blue), acridines (e.g. acridine orange, chloroflavin, acriflavine), acridine Ketones (e.g. acridinone, 10-butyl-2-chloroacridone), anthraquinones (e.g. anthraquinone), squaric acid compounds (e.g. squaric acid compounds), styryl groups, basic styrene Bases (for example 2-{2-[4-(dimethylamino)phenyl]vinyl}benzoxazole), coumarins (for example 7-diethylamino-4-methyl incense Coumarin, 7-hydroxy-4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H[1]benzopyrano[6,7,8 -ij] quinazin-11-one).

Among these sensitizers, polynuclear aromatics, acridones, styryls, basic styryls, coumarins are preferred, and polynuclear aromatics are more preferred. Polynuclear aromatic Among the aromatics, anthracene derivatives are the best.

The content of the sensitizer is preferably 0 parts by mass to 1,000 parts by mass, more preferably 10 parts by mass to 500 parts by mass, and more preferably 50 parts by mass with respect to 100 parts by mass of the photoacid generator B1 or the quinonediazide compound B2. ~200 parts by mass.

In addition, one kind of sensitizer may be used alone, or two or more kinds may be used in combination.

[Basic compound]

The resin composition of the present invention may contain a basic compound.

As the basic compound, it can be used arbitrarily selected from those used in the chemically amplified hardening composition. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxide, and quaternary ammonium salts of carboxylic acids. As specific examples of these, the compounds described in paragraphs 0204 to 0207 of Japanese Patent Laid-Open No. 2011-221494 can be cited.

Specifically, examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and bicyclic Hexamine, dicyclohexylmethylamine, etc.

Examples of aromatic amines include aniline, benzylamine, N,N-dimethylaniline, and dianiline.

Examples of heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, and N- Methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, smoke Alkali, nicotinic acid, nicotinamide, quinoline, 8-hydroxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, Piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N'-[2-(4-morpholinyl)ethyl]thiourea, 1,5-diazabicyclo[4.3.0] -5-nonene, 1,8-diazabicyclo[5.3.0]-7-undecene, butane-1,2,3,4-tetracarboxylic acid tetra(1,2,2,6, 6-pentamethyl-4-piperidinyl) ester and the like.

Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.

Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

Among these, a heterocyclic amine is preferred, and N-cyclohexyl-N'-[2-(4-morpholinyl)ethyl]thiourea is particularly preferred.

The basic compound may be used alone or in combination of two or more.

In addition, the content when the basic compound is contained relative to 100 parts by mass of the total solid content in the resin composition is preferably 0.001 to 3 parts by mass, more preferably 0.05 to 0.5 parts by mass.

[Surfactant]

The resin composition of the present invention may contain a surfactant.

As the surfactant, any of anionic, cationic, nonionic, or amphoteric can be used, and a preferred surfactant is a nonionic surfactant. As the surfactant, a nonionic surfactant is preferable, and a fluorine surfactant is more preferable.

Examples of the surfactant that can be used in the first aspect include, for example, commercially available Megafac F142D, Megafac F172, Megafac F173, Megafac F176, and Mega Method (Megafac) F177, Megafac F183, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781, Megafac F781 -F, Megafac R30, Megafac R08, Megafac F-472SF, Megafac BL20, Megafac R-61, Megafac R-90 (Made by DIC (shares)), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC- 431, Novec FC-4430 (Sumitomo 3M Co., Ltd.), Asahi Guard AG7105, Asahi Guard AG7000, Asahi Guard AG950, Asahi Guard AG7600, Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S- 145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-103, Surflon SC- 104, Surflon SC-105, Surflon SC-106 (manufactured by Asahi Glass Co., Ltd.), Eftop EF351, Eftop EF352, Eftop ) EF801, Eftop (Eftop) EF802 (Mitsubishi Materials Electronics Co., Ltd.), Ftergent 250 (Neos (NEOS)). In addition to the above, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and Eftop (Mitsubishi Materials Electronics Co., Ltd.) (Manufactured by shares), Megafac (manufactured by DIC), and Fluorad (Sumitomo 3M) Manufacture), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA) and other series.

In addition, as the surfactant, the compounds described in paragraphs 0151 to 0155 of Japanese Patent Laid-Open No. 2014-238438 can also be cited as preferred examples.

The content when the surfactant is contained relative to 100 parts by mass of the total solid content of the resin composition is preferably 0.001 to 5.0 parts by mass, more preferably 0.01 to 2.0 parts by mass.

The surfactant may contain only one kind, or two or more kinds. When two or more cases are included, the total amount is preferably within the above range.

[Adhesion improver]

The resin composition of the present invention may contain an adhesion improver.

Examples of the adhesion modifier include alkoxysilane compounds.

The alkoxysilane compound is preferably a compound that improves the adhesion of an inorganic substance that becomes a base material, such as silicon compounds such as silicon, silicon oxide, and silicon nitride, and metals such as gold, copper, molybdenum, titanium, and aluminum, to the insulating film.

Specific examples of the adhesion improver include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ- Methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacrylonitrile Propylpropylmethyl diethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, β-( 3,4- (Epoxycyclohexyl) ethyl trimethoxy silane, vinyl trimethoxy silane, etc. Among these, γ-glycidoxypropyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane are preferred, and γ-glycidoxypropyltrimethoxysilane is more preferred. . These can be used alone or in combination of two or more.

The content of the adhesion modifier is preferably 0.001 to 15 parts by mass, more preferably 0.005 to 10 parts by mass relative to 100 parts by mass of the total solid content of the resin composition. Only one kind of adhesion improver may be used, or two or more kinds may be used. When two or more types are used, the total amount is preferably within the above range.

[Antioxidants]

The resin composition of the present invention may contain an antioxidant.

As the antioxidant, a known antioxidant may be contained. By adding an antioxidant, it can prevent the coloring of the cured film, or can reduce the reduction in the thickness of the film due to decomposition, and has the advantages of excellent heat resistance and transparency.

Examples of such antioxidants include phosphorus antioxidants, amides, hydrazines, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, and nitrite , Sulfite, thiosulfate, hydroxylamine derivatives, etc. Among these, from the viewpoint of coloring of the cured film and reduction in film thickness, particularly preferred are phenol-based antioxidants, amide-based antioxidants, hydrazine-based antioxidants, and sulfur-based antioxidants, and most preferred are phenol-based antioxidants . These antioxidants may be used alone or in combination of two or more.

As specific examples, the compounds described in paragraphs 0026 to 0031 of Japanese Patent Laid-Open No. 2005-29515 can be cited, and these contents are incorporated into this application. In the book.

Examples of commercially available products of phenolic antioxidants include Adekastab AO-15, Adekastab AO-18, Adekastab AO-20, Adekastab AO-23, Adekastab AO-30, Adekastab AO-37, Adekastab AO-40, Eddy Adekastab AO-50, Adekastab AO-51, Adekastab AO-60, Adekastab AO-70, Adekastab Adekastab AO-80, Adekastab AO-330, Adekastab AO-412S, Adekastab AO-503, Adekastab ( Adekastab) A-611, Adekastab A-612, Adekastab A-613, Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-8W, Adekastab PEP-24G, Adekastab PEP-36, Adekastab PEP-36 36Z, Adekastab HP-10, Adekastab 2112, Adekastab 260, Adekastab 522A, Adekastab 522A Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010, Adekastab (10 Adekastab) TPP, Adekastab CDA-1, Adekastab CDA-6, Adekastab ZS-27, Adekastab ZS-90, Adekastab ZS-91 (the above is ADEKA) )), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox MD1024, Irganox 1035FF, Yi Irganox 1035, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox ) 1726, Irgafos 168, Irgamod 295 (made by BASF), Tinuvin 405 (made by BASF), etc. Among them, Adekastab AO-60, Adekastab AO-80, Irganox 1726, Irganox 1035, Yilu can be suitably used Irganox 1098, Tinuvin 405.

The content when the antioxidant is contained is preferably 0.1% by mass to 10% by mass, more preferably 0.2% by mass to 5% by mass, and particularly preferably 0.5% by mass relative to 100 parts by mass of the total solid content of the resin composition. 4% by mass. By setting to this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good.

[Other ingredients]

The resin composition of the present invention may include an ultraviolet absorber, a metal deactivator, or an acid multiplying agent, a development accelerator, a plasticizer, a thermal free radical generator, a thermal acid generating agent, Thickener, and organic or inorganic anti-settling Well-known additives. In addition, as these compounds, for example, reference can be made to the descriptions in paragraphs 0201 to 0224 of Japanese Patent Laid-Open No. 2012-88459 and Japanese Patent Laid-Open No. 2014-238438, and these contents are incorporated into the specification of the present application in.

In addition, as other additives, thermal radical generators described in paragraphs 0120 to 0121 of Japanese Patent Laid-Open No. 2012-8223, nitrogen-containing compounds described in International Publication No. 2011/136074, and thermal acid generation can also be used Agent, and incorporate these contents into the specification of this application.

[Preparation method of photosensitive resin composition]

The resin composition of the present invention can be prepared by mixing the components at a predetermined ratio and stirring and dissolving by any method. For example, the photosensitive resin composition of the present invention may be prepared by preparing solutions in which each component is dissolved in a solvent in advance, and then mixing these solutions at a predetermined ratio. The composition solution prepared as described above can also be used after being filtered using, for example, a filter with a pore size of 0.2 μm.

[Manufacturing method of cured film]

The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).

(1) The step of applying the resin composition of the present invention containing the organic solvent D on the substrate (coating step); (2) The step of removing the organic solvent D from the applied resin composition (solvent removal step); (3) Using active radiation to enter the resin composition from which the organic solvent D has been removed The step of line exposure (exposure step); (4) The step of developing the exposed resin composition with a developing solution (developing step); (5) Step of thermally curing the developed resin composition to obtain a cured film (post-baking step).

The steps are explained in order below.

In the step (1), it is preferable to apply the resin composition of the present invention on a substrate to prepare a wet film containing a solvent.

Before performing the step (1), the substrate may be cleaned by alkaline cleaning or plasma cleaning. In addition, the cleaned substrate can also be treated with hexamethyldisilazane or the like. The method of treating the surface of the substrate with hexamethyldisilazane is not particularly limited, and examples include a method of exposing the substrate to hexamethyldisilazane vapor.

Examples of the substrate include an inorganic substrate, a resin substrate, and a substrate using a composite material of a resin material and an inorganic material.

Examples of inorganic substrates include glass substrates, quartz substrates, silicon substrates, silicon nitride substrates, and composite substrates on which molybdenum, titanium, aluminum, and copper are deposited on these substrates.

Examples of the resin substrate include substrates containing the following resins: polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, Polycarbonate, polysulfonate, polyethersulfonate, polyarylate, allyl diethylene glycol carbonate, polyamide, polyimide, polyamide imide, polyether imide, Fluorine resins such as polybenzoxazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanide Synthetic resins such as ester resins, crosslinked fumarate diesters, cyclic polyolefins, aromatic ethers, maleimide-olefins, cellulose, and episulfide compounds.

These substrates can also form a multi-layer build-up structure such as a thin film transistor (TFT) element according to the shape of the final product.

The method of applying the resin composition to the substrate is not particularly limited, and for example, methods such as a slit coating method, a spray method, a roll coating method, a spin coating method, a cast coating method, a slit, and a spin method can be used.

In the case of the slit coating method, it is preferable to set the relative moving speed of the substrate and the slit die to 50 mm/sec to 120 mm/sec.

The wet film thickness when applying the resin composition is not particularly limited, and can be applied with a film thickness corresponding to the application. For example, it is preferably 0.5 μm to 10 μm.

Before applying the resin composition of the present invention on a substrate, a so-called pre-wet method as described in Japanese Patent Laid-Open No. 2009-145395 may also be applied.

In the step (2), the solvent is removed from the wet film formed by coating the resin composition by reduced pressure (vacuum) and/or heating, etc. to form a dry film on the substrate. The heating conditions in the solvent removal step are preferably about 30 seconds to 300 seconds at 70°C to 130°C. When the temperature and time are within the above range, the adhesion of the pattern is better when the step (4) described later is performed, and the residue may be further reduced.

In the step (3), a predetermined pattern is irradiated on the substrate provided with the dried film Actinic rays. In this step, acid groups such as carboxyl groups or phenolic hydroxyl groups are generated in the exposed portion to increase the solubility of the exposed portion in the developer.

That is, in an aspect including a polymer component and a photoacid generator, the photoacid generator decomposes to generate an acid by irradiation with actinic rays, and the polymer component includes an acid group protected by an acid decomposable group The constituent unit of the group. Furthermore, by the catalytic action of the generated acid, the acid-decomposable group contained in the dried film is hydrolyzed to generate a carboxyl group or a phenolic hydroxyl group.

In addition, in the aspect containing a quinonediazide compound, the quinonediazide compound generates a carboxyl group by irradiation with actinic rays.

As a light source for actinic rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generating device, etc. can be used, and i-ray can be preferably used (365 nm), h-rays (405 nm), g-rays (436 nm), and other actinic rays having a wavelength of 300 nm or more and 450 nm or less. In addition, if necessary, the irradiation light may be adjusted by a spectral filter such as a long-wavelength cut filter, a short-wavelength cut filter, or a band-pass filter. The exposure amount is preferably 1 mJ/cm ² to 500 mJ/cm ² .

As an exposure device, a mirror projection aligner (mirror projection aligner), a stepper (scanner), a scanner (proximity), a contact (contact), a microlens array (microlens array), Various types of exposure machines such as lens scanners and laser exposures. In addition, exposure using so-called super-resolution technology can also be performed. Examples of the super-resolution technique include multiple exposures that perform multiple exposures, a method using a phase shift mask, and a ring-band illumination method. By making It is better to use these super-resolution technologies to form higher and finer patterns.

In the step (4), the resin composition is developed using a developing solution. A positive image is formed by removing the area of the exposed portion having acid groups that is easily dissolved in the developer.

The developing solution used in the developing step is preferably an aqueous solution containing a basic compound. As the basic compound, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; sodium bicarbonate, potassium bicarbonate Alkali metal bicarbonates; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, diethyldimethylammonium hydroxide and other tetraoxane hydroxide Ammonium hydroxides; hydroxyalkyl trialkylammonium hydroxides such as choline; silicates such as sodium silicate and sodium metasilicate; alkylamines such as ethylamine, propylamine, diethylamine, and triethylamine Alcohols such as dimethylethanolamine and triethanolamine; 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0]- 5-Nonene and other alicyclic amines.

Among these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline (hydroxide-2 -Hydroxyethyltrimethylammonium).

In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of the alkali may be used as a developing solution.

The pH value of the developer is preferably 10.0 to 14.0.

The development time is preferably 30 seconds to 500 seconds, and the development method may be any of a puddle method, a spray method, and a dipping method.

After development, a rinse step can also be performed. In the rinsing step, by removing the developed substrate with pure water or the like, the attached developer is removed and the developing residue is removed. As the rinsing method, a known method can be used. For example, spray shower, dipping shower, etc. can be mentioned.

In the step (5), by heating the obtained positive image, the acid-decomposable group is thermally decomposed to generate an acid group such as a carboxyl group or a phenolic hydroxyl group, which is cross-linked with a cross-linkable group, a cross-linking agent, etc. In this way, a hardened film can be formed. This heating is preferably performed using a heating device such as a hot plate or an oven. The heating temperature is preferably 200°C to 350°C, more preferably 250°C to 350°C. Regarding the heating time, it is preferably 5 minutes to 90 minutes for a hot plate, and 30 minutes to 120 minutes for an oven. By performing cyclization reaction or cross-linking reaction by heating, a more excellent cured film such as heat resistance and hardness can be formed. In addition, the heat treatment is carried out under a nitrogen atmosphere, whereby the transparency can be further improved.

Before post-baking, post-baking may be performed after baking at a relatively low temperature (additional middle baking step). In the case of ongoing baking, it is preferable to perform post-baking at a high temperature of 200° C. or higher after heating at 90° C. to 150° C. for 1 to 60 minutes. In addition, the middle baking and the post-baking may be divided into three or more stages to be heated. By setting such middle baking and post baking, the cone angle of the pattern can be adjusted. For the heating of these baking, a known heating method such as a hot plate, an oven, and an infrared heater can be used.

Furthermore, before post-baking, and after the entire surface of the patterned substrate is re-exposed (post-exposure) by actinic rays, post-baking can be performed, whereby light existing in the unexposed portion can be removed The acid generator generates acid and functions as a catalyst to promote the cross-linking step, thereby promoting the hardening reaction of the film. As a preferable exposure amount when the post-exposure step is included, it is preferably 100 mJ/cm ² to 3,000 mJ/cm ² , and particularly preferably 100 mJ/cm ² to 500 mJ/cm ² .

The cured film obtained from the resin composition of the present invention can also be used as a dry etching resist. When the cured film obtained by thermal curing in the post-baking step is used as a dry etching resist, as the etching process, dry etching processes such as ashing, plasma etching, and ozone etching may be performed.

In addition, from the viewpoint of making the obtained cured film function as an alignment film, the method for producing a cured film of the present invention preferably performs a light alignment process after the post-baking step.

The light alignment treatment is not particularly limited except that light having a wavelength of 313 nm or less is used, and in terms of obtaining uniform alignment, it is preferable to use polarized ultraviolet light. In this case, the method of irradiating polarized ultraviolet rays is not particularly limited. In addition, the polarized light is not particularly limited, and examples thereof include linear polarized light, circular polarized light, and elliptical polarized light. Among them, linear polarized light is preferred.

In addition, as long as the polarized light is substantially obtained, unpolarized light may be irradiated at a certain angle from the normal line of the thin film. In other words, unpolarized light may be irradiated from the oblique direction of the surface of the cured film. The term "inclined irradiation" is not particularly limited as long as the direction of the polar angle θ (0°<θ<90°) is inclined with respect to the normal direction of the surface of the cured film, and can be appropriately selected according to the purpose. It is preferably 20°~80°.

Examples of light sources used include xenon lamps and high-pressure mercury. Lamps, ultra-high pressure mercury lamps, metal halide lamps, etc.

By using an interference filter, a color filter, or the like for ultraviolet rays obtained from such a light source, the wavelength range of irradiation can be limited. In addition, linear polarization can be obtained by using a polarizing filter or a polarizing filter for the light from these light sources.

[Hardened film]

The cured film of the present invention is a cured film obtained by curing the resin composition of the present invention. In addition, the cured film of the present invention is preferably a cured film obtained by the method of forming the cured film of the present invention.

The cured film of the present invention can be suitably used as an interlayer insulating film and a protective film. Especially when it is used as an interlayer insulating film, by performing an optical alignment process in advance, the cured film also has a function as an alignment film, and therefore can be used for a liquid crystal display device described later.

[Liquid crystal display device]

The liquid crystal display device of the present invention has the cured film of the present invention.

The liquid crystal display device of the present invention is not particularly limited as long as the interlayer insulating film formed using the resin composition of the present invention is used, and can be applied to a known liquid crystal display device employing various structures. In addition, the interlayer insulating film formed using the resin composition of the present invention can also serve as an alignment film, so that the alignment film can be eliminated from a known liquid crystal display device.

For example, specific examples of thin film transistors (TFTs) included in the liquid crystal display device of the present invention include amorphous silicon-TFTs, low-temperature polysilicon-TFTs, and oxide semiconductor TFTs. Since the cured film of the present invention is excellent in electrical characteristics, it can be compared with These TFTs are preferably used in combination.

In addition, as a preferable liquid crystal driving method of the liquid crystal display device of the present invention, a twisted nematic (TN) method, a vertical alignment (VA) method, and an in-plane switching (IPS) method are included. ) Method, fringe field switching (FFS) method, optically compensated bending (Optically Compensated Bend, OCB) method, etc.

Regarding the panel configuration, the cured film of the present invention can also be used in a color filter on array (COA) type liquid crystal display device, for example, it can be used as an organic insulator of Japanese Patent Laid-Open No. 2005-284291 The film (115), or the organic insulating film (212) of Japanese Patent Laid-Open No. 2005-346054.

In addition, the resin composition of the present invention and the cured film of the present invention are not limited to the above applications, and can be used in various applications. For example, in addition to the interlayer insulating film, it can also be suitably used as a protective film for a color filter, a spacer for holding the liquid crystal layer in a liquid crystal display device to a certain thickness, or a solid imaging element Microlenses on color filters, etc.

For details of the liquid crystal display device, refer to the descriptions in Japanese Patent Laid-Open No. 2007-328210 and Japanese Patent Laid-Open No. 2014-238438, and incorporate this content into this specification.

[Example]

Hereinafter, the present invention will be further described in detail based on examples. The materials, usage amounts, ratios, processing contents, processing order, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Thus, the scope of the invention It should not be interpreted in a limited way by the embodiments shown below. Furthermore, as long as there is no special explanation, "parts" and "%" are quality standards.

[Synthesis of constituent unit (monomer a-1) having photo-alignment group]

Methyl trans-4-hydroxycinnamate (manufactured by Tokyo Chemical Industry Co., Ltd., 12.5g, 0.07mol) and triethylamine (manufactured by Wako Pure Chemical Industries, Ltd., 7.79g, 0.07mol) were dissolved in tetrahydrofuran in advance (Hereinafter referred to as "THF") In 100 mL, after cooling to 0°C, methacryloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd., 7.33 g, 0.07 mol) was slowly added dropwise.

Then, 500 g of water was added to the reaction system that became cloudy, and after stirring for 1 hour, it was filtered to obtain 14 g of monomer a-1 having a cinnamate group as a photo-alignment group. The structure was confirmed by nuclear magnetic resonance (NMR).

[Synthesis of constituent unit (monomer a-2) having photo-alignment group]

4-Hydroxy-3-methoxycinnamic acid ethyl ester (manufactured by Tokyo Chemical Industry Co., Ltd., 22.2 g, 0.1 mol) was dissolved in 150 mL of dimethylacetamide in advance, and potassium carbonate (Wako Pure Chemical Industries ( Strand), manufacture, 30g, 0.22mol), and raise the temperature to 90°C.

Then, 4-chlorobutanol (manufactured by Wako Pure Chemical Industries, Ltd., 21.6 g, 0.2 mol) was added dropwise and stirred for 3 hours.

After that, the reaction solution was poured into 1 L of water, neutralized with 2N HCL, extracted with 700 mL of ethyl acetate, washed with saturated saline, and concentrated.

Then, it was fractionated by silica gel column chromatography to obtain 23 g of an intermediate compound.

15 g (0.05 mol) of the intermediate compound and triethylamine (manufactured by Wako Pure Chemical Industries, Ltd., 5.6 g, 0.056 mol) were dissolved in 100 mL of THF, and cooled to 0°C.

Then, methacryloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd., 5.8 g, 0.056 mol) was added dropwise, and after stirring for 3 hours, the reaction solution was poured into 500 g of water, extracted with ethyl acetate, and then concentrated.

Then, it was separated by silica gel column chromatography to obtain 20 g of monomer a-2 having a spacer cinnamate as a photo-alignment group.

[Synthesis of constituent unit (monomer a-3) having photo-alignment group]

Hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd., 63.8 g, 0.58 mol) was dissolved in 500 mL of dimethylacetamide in advance, and potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd., 40 g, 0.29 mol) was added ), and raise the temperature to 90 ℃.

Then, 4-chlorobutyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., 25.6 g, 0.145 mol) was added dropwise and stirred for 3 hours.

After that, the reaction solution was poured into 1 L of water, neutralized with 2N HCL, extracted with 700 mL of ethyl acetate, washed with saturated saline, and concentrated. The crude crystals were taken out and separated by silica gel column chromatography to obtain 18 g of an intermediate compound.

18 g of this intermediate compound and triethylamine (manufactured by Wako Pure Chemical Industries, Ltd., 7.79 g, 0.07 mol) were dissolved in 100 mL of THF, and cooled to 0°C.

Then, cinnamyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd., 13.1 g, 0.07 mol) was added dropwise, and after stirring for 3 hours, the reaction solution was poured into 500 g of water, extracted with ethyl acetate, and then concentrated.

Then, it was fractionated by silica gel column chromatography to obtain 22 g of monomer a-3 having a chalcone group as a photo-alignment group.

[Synthesis of constituent unit (monomer a-4) having photo-alignment group]

The monomer a-4 having an azo group as a photo-alignment group was synthesized in the same manner as "Macromolecules" (2004, Vol. 37, #7, p. 2572).

[Synthesis of constituent unit (monomer a-5) having photo-alignment group]

Synthesize coumarin in the same way as "Journal of Polymer Science, Part A: Polymer Chemistry" (2010, Vol. 48, #19, 4323) The monomer a-5 as a photo-alignment group.

[Synthesis of structural unit (monomer e-1) protected by acid-decomposable group]

Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., 86 g, 1 mol) was cooled to 15° C. in advance, and camphorsulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd., 4.6 g, 0.02 mol) was added.

Then, 2-dihydrofuran (manufactured by Kawaken Fine Chemicals Co., Ltd., 71 g, 1 mol, 1.0 equivalent) was added dropwise to the reaction solution.

After stirring for 1 hour, saturated sodium bicarbonate (500 mL) was added, and extraction was performed with ethyl acetate (500 mL).

Then, after drying with magnesium sulfate, the insoluble matter was filtered, and then at 40 ℃ The following is concentrated under reduced pressure, and the yellow oil as the residue is distilled under reduced pressure, thereby obtaining 125 g of methacrylic acid with a boiling point (bp.) of 54°C to 56°C/3.5 mmHg as a colorless oily substance. Tetrahydro-2H-furan-2-yl ester as monomer e-1 (80% yield).

[Synthesis of constituent unit (monomer e-2) protected by acid group with acid-decomposable group]

Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., 86 g, 1 mol) was cooled to 15° C. in advance, and camphorsulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd., 4.6 g, 0.02 mol) was added.

Then, ethyl vinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., 74 g, 1 mol, 1.0 equivalent) was added dropwise to the reaction solution.

After stirring for 1 hour, saturated sodium bicarbonate (500 mL) was added, and extraction was performed with ethyl acetate (500 mL).

Then, after drying with magnesium sulfate, the insoluble matter was filtered, and then concentrated under reduced pressure at 40° C. or lower, and the yellow oily substance as a residue was distilled under reduced pressure, whereby 125 g of colorless oily substance was obtained. Ethoxyethyl methacrylate with boiling point (bp.) 50℃~52℃/3.5mmHg fraction is used as monomer e-2 (yield 78%).

[Synthesis of polymer (P1) having constituent unit s1]

Under a nitrogen stream, 22 g of diethylene glycol methyl ethyl ether (hereinafter referred to as "HS-EDM") was heated and stirred to 70°C. The synthesized monomer a-1 (11.1g, 45mol%), hexafluoroisopropyl methacrylate (hereinafter referred to as "HFIP") (manufactured by Tokyo Chemical Industry Co., Ltd., 3.5g, 15mol) was added dropwise over 2 hours %), methacrylic acid (hereinafter referred to as "MAA") (Wako Pure Chemical Industries, Ltd., 1.7g, 20mol%), glycidyl methacrylate (hereinafter referred to as "GMA") (Wako Pure Chemical Industries, Ltd., 2.8g, 20mol %), a free radical polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) 497 mg (2 mol%), and a mixed solution of PGMEA (30 g). After the dropwise addition, the reaction was further performed at 70° C. for 4 hours, thereby obtaining a PGMEA solution (solid content concentration: 27%) having the polymer P1 constituting the unit s1.

[Synthesis of polymer (P2 to P15) having constituent unit s1]

The polymer P2 to the polymer P15 were synthesized in the same manner as the polymer P1 except that the types of monomers, initiators, and solvents were changed according to the following Table 1. In addition, the numerical value described in the column of each single body component in the following Table 1 is the usage amount (mol%) of each single body with respect to the total amount of single body components. In addition, the numerical value described in the column of the polymerization initiator is the mol% when the total amount of the single body components is set to 100 mol%. In addition, the abbreviations used in the examples are as follows.

<abbreviation>

. HFIP: hexafluoroisopropyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

. 6FM: Trifluoroethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

. KBM-503: 3-Methylacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

. C18MA: octadecyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

. MAA: methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)

. MMA: methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

. St: Styrene (manufactured by Wako Pure Chemical Industries, Ltd.)

. AA: Acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)

. GMA: glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

. OXE-30: (3-ethyloxetan-3-yl) methyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

. DCPM: Dicyclopentyl methacrylate (Fancryl FA-513M, manufactured by Hitachi Chemical Co., Ltd.)

. NBMA: N-butoxymethacrylamide (manufactured by Mitsubishi Rayon)

. V-601: Radical polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd.)

. V-65: Radical polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd.)

. PGMEA: methoxypropanediol acetate (made by Daicel Corporation)

. HS-EDM: Diethylene glycol methyl ethyl ether (manufactured by Toho Chemical Industry Co., Ltd.)

[Table 1]

[Synthesis of other photo-alignment polymers]

<Synthesis of polymer P16>

The polymer P16 was obtained by the same method as the specific copolymer P1 described in paragraph [0084] (Synthesis Example 1) of WO2010/150748.

<Synthesis of polymer P17>

The polymer P17 was synthesized in the same manner as the photo-alignment polymer (A-1) described in paragraph [0161] (Preparation Example 1) of Japanese Patent Laid-Open No. 2013-177561.

[Preparation of polymers with other constituent units]

<Synthesis of polymer A-1 comprising a structural unit a1 having a group having an acid group protected by an acid-decomposable group and a structural unit a2 having a crosslinkable group>

Under nitrogen flow, the HS-EDM (82 parts) was heated and stirred to 90°C.

Then, tetrahydro-2H-furan-2-yl methacrylate synthesized as monomer e-1 (43 parts (equivalent to 40.5 mol% in all single-volume body components)) and OXE were added dropwise over 2 hours -30 (48 parts (equivalent to 37.5 mol% in all single body components)), MAA (6 parts (equivalent to 9.5 mol% in all single body components)), hydroxyethyl methacrylate (Wako Pure Manufactured by the pharmaceutical industry (shares), a mixed solution of 11 parts (equivalent to 12.5 mol% in all single-body components), radical polymerization initiator V-601 (4.3 parts), and PGMEA (82 parts), and The reaction was carried out at 90°C for 2 hours, whereby a solution of polymer A-1 (solid content concentration: 40%) was obtained.

In addition, the weight average molecular weight of the obtained polymer A-1 measured by gel permeation chromatography (GPC) was 15,000.

<Synthesis of polymer A-2 comprising structural unit a1 having an acid group protected by an acid-decomposable group>

PGMEA (238g) was heated and stirred to 90°C under a nitrogen stream.

Then, over 2 hours, tetrahydro-2H-furan-2-yl methacrylate (240 g (equivalent to 61.1 mol% of all single-volume body components)) synthesized as monomer e-1 was added dropwise. 50.4g (equivalent to 17.6mol% in all single body components), MMA (27.9g (equivalent to 21.3mol% in all single body components)), free radical polymerization initiator V-601 (14.7g ), and a mixed solution of PGMEA (238 g), and further reacted at 90° C. for 2 hours. After cooling, PGMEA (42 g) was added to obtain a solution of polymer A-2 (solid content concentration: 38%).

The weight average molecular weight of the obtained polymer A-2 measured by gel permeation chromatography (GPC) was 15,000.

<Synthesis of polymer A-3 containing structural unit a3 having a crosslinking group>

Under nitrogen flow, the HS-EDM (145 g) was heated and stirred to 70°C.

Then, GMA (144.7g (67.9mol%)), MAA (16.7g (12.9mol%)), St (28.1g (18.0mol%)), DCPM (3.87g (1.17mol%)) were added dropwise over 2 hours , A mixed solution of free radical polymerization initiator V-65 (20.8g (5.6mol% conversion of monomer amount)), and HS-EDM (145g).

After the dropwise addition, the reaction was performed at 70° C. for 4 hours, thereby obtaining a PGMEA solution of polymer A-3 (solid content concentration: 35%).

<Contains a structural unit a3 having an acid group and a structure having a crosslinkable group Polymer A-4 of unit a2>

After replacing the inside of the flask with nitrogen, 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2′-azobisisobutyronitrile was dissolved was added.

Then, after adding St (22.5g), MAA (45.0g), DCPM (67.5g), and GMA (90.0g), the stirring was started slowly.

Then, the temperature of the solution was raised to 80°C, and after maintaining this temperature for 5 hours, the temperature was heated at 90°C for 1 hour to complete the polymerization.

Thereafter, the reaction product solution was added dropwise to a large amount of water to coagulate the reactant. After washing this coagulated substance with water, it was redissolved in THF (200 g) and coagulated again with a large amount of water.

After performing the operations of re-dissolution and coagulation three times in total, the obtained coagulated product was dried under reduced pressure at 60° C. for 48 hours to obtain polymer A-4. Thereafter, a solution of polymer A-4 was prepared using diethylene glycol so that the solid content concentration became 25% by weight.

<Polymer A-5 containing a structural unit a3 having an acid group>

Under nitrogen flow, the HS-EDM (11 g) was heated and stirred to 70°C.

Then, MAA (4.3g (50.0mol%)), MMA (5.0g (50.0mol%)), radical polymerization initiator V-601 (0.497g (conversion of 2mol% monomer amount)) was added dropwise over 2 hours , And HS-EDM (11g) mixed solution.

After the dropwise addition, the reaction was carried out at 90°C for 2 hours, thereby obtaining a solution of polymer A-5 (solid content concentration: 30%).

<Polymer A-6 containing a structural unit having an acid group and a structural unit having a crosslinking group>

Under nitrogen flow, the HS-EDM (91 g) was heated and stirred to 70°C.

Then, OXE-30 (75g (67.9mol%)), MAA (6.7g (12.9mol%)), St (11.3g (18.0mol%)), DCPM (1.5g (1.17mol%)) were added dropwise over 2 hours ), a mixed solution of radical polymerization initiator V-65 (4.5 g (3.0 mol% conversion of monomer amount)), and HS-EDM (91 g).

After the dropwise addition, the reaction was carried out at 70° C. for 4 hours, thereby obtaining a solution of polymer A-6 (solid content concentration: 30%).

<Synthesis of non-optical alignment polymer A-7>

The non-optical alignment polymer A- was synthesized in the same manner as the non-optical alignment polymer (E-1) described in paragraph [0165] (Preparation Example 5) of Japanese Patent Laid-Open No. 2013-177561 7.

[Crosslinking agent]

Use the following as the crosslinking agent.

<C-1>

A polyfunctional epoxy compound (EX-321L, manufactured by Nagase ChemteX) is used as the cross-linking agent C-1 with a molecular weight of 1,000 or less.

<HMM>

Hexamethoxymethyl melamine (HMM, manufactured by Tokyo Chemical Industry Co., Ltd.)

[Acid generator]

Synthesize or use the following as an acid generator (photoacid generator and thermal acid generator Raw materials).

<Synthesis of B-1>

To a suspension solution of 2-naphthol (10 g) and chlorobenzene (30 mL), aluminum chloride (10.6 g) and 2-chloropropyl acetyl chloride (10.1 g) were added, and the mixture was heated to 40° C. and reacted for 2 hours. Under cooling in an ice bath, a 4N HCL aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added to perform liquid separation. Potassium carbonate (19.2g) was added to the organic layer, and after reacting at 40°C for 1 hour, 2N aqueous HCL solution (60mL) was added to perform liquid separation. After the organic layer was concentrated, the crystals were crystallized with diisopropyl ether (10mL) It was slurried again, filtered and dried to obtain a ketone compound (6.5 g).

To the obtained suspension solution of the ketone compound (3.0 g) and methanol (30 mL), acetic acid (7.3 g) and a 50% by mass aqueous hydroxylamine solution (8.0 g) were added and heated to reflux. After leaving to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and then dried to obtain an oxime compound (2.4 g).

The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature and reacted for 1 hour. Water (50 mL) was added to the reaction liquid, and the precipitated crystals were filtered, then re-slurryed with methanol (20 mL), filtered, and dried to obtain B-1 (2.3 g).

Furthermore, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-1 is δ=8.3(d,1H),8.0(d,2H),7.9(d,1H),7.8(d,1H),7.6 (dd,1H),7.4(dd,1H),7.3(d,2H),7.1(d,1H),5.6(q,1H),2.4(s,3H),1.7(d,3H).

<Synthesis of B-2>

4.0 g of 1-amino-2-naphthol hydrochloride was suspended in 16 g of N-methylpyrrolidone, and after adding 3.4 g of sodium bicarbonate, 4,4-dimethyl-3-oxopentane was added dropwise 4.9 g of methyl acid ester was heated at 120°C for 2 hours under a nitrogen atmosphere. After leaving to cool, water and ethyl acetate were added to the reaction mixture and the liquid was separated. The organic layer was dried with magnesium sulfate, filtered, and concentrated to obtain crude B-2A. The crude B-2A was purified by silica gel column chromatography to obtain 1.7 g of intermediate B-2A.

B-2A (1.7g) and p-xylene (6mL) were mixed, 0.23g of p-toluenesulfonic acid monohydrate was added, and it heated at 140 degreeC for 2 hours. After leaving to cool, water and ethyl acetate were added to the reaction mixture to perform liquid separation, the organic layer was dried with magnesium sulfate, and then filtered and concentrated to obtain crude B-2B.

THF (2 mL) was mixed with the total amount of crude B-2B, 6.0 mL of 2M hydrochloric acid/THF solution was added dropwise with ice bath cooling, followed by dropwise addition of isoamyl nitrite (0.84 g), and the temperature was raised to room temperature (25°C ) After stirring for 2 hours. Water and ethyl acetate were added to the obtained reaction mixture and liquid separation was performed. After the organic layer was washed with water, it was dried with magnesium sulfate, filtered, and concentrated to obtain crude intermediate B-2C.

The total amount of crude intermediate B-2C was mixed with acetone (10 mL), and triethylamine (1.2 g) and p-toluenesulfonyl chloride (1.4 g) were added under ice cooling, and the temperature was raised to room temperature and stirred for 1 hour. . Water and ethyl acetate were added to the resulting reaction mixture and the liquid was separated. After the organic layer was dried with magnesium sulfate, it was filtered and concentrated to obtain crude B-2. After re-slurrying crude B-2 with cold methanol, it was filtered and dried to obtain B-2 (1.2 g).

Furthermore, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-2 is δ=8.5-8.4(m, 1H), 8.0-7.9(m, 4H), 7.7-7.6(m, 2H), 7.6- 7.5 (m, 1H), 7.4 (d, 2H), 2.4 (s, 3H), 1.4 (s, 9H).

<B-3>

A commercially available acid generator (PAG-103, manufactured by BASF) was used.

<Compound B-4 of the structure shown below>

It was synthesized according to the method described in paragraph No. 0128 of WO2011/087011.

<Compound B-5 of the structure shown below>

Commercially available triarylcarbamate salt (GSID-26-1, manufactured by BASF) [Chem. 34]

<TAS-200>

Quinonediazide compound (TAS-200, manufactured by Toyo Synthetic Industries Co., Ltd.)

<PTSA>

As the thermal acid generator, p-toluenesulfonic acid monohydrate (PTSA, manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

[Other ingredients]

<Basic compound F-1>

As the basic compound, a compound having the following structure is used.

<F-554>

Use non-ionic surfactants containing perfluoroalkyl groups (F-554, DIC) (Co., Ltd.) as a surfactant.

<KBM-403>

Γ-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was used as an adhesion modifier.

[Example 1 to Example 74 and Comparative Example 1 to Comparative Example 4]

Each component shown in the following Table 2 was dissolved and mixed in a solvent (PGMEA) until the solid content concentration became 18% by mass, and filtered through a filter made of polytetrafluoroethylene with a diameter of 0.2 μm to obtain each example and comparison Example photosensitive resin composition. In addition, the addition amount in a table shows the addition amount based on the solid content of each component, and a unit is a mass part.

[Table 2]

[Patternized Evaluation]

<sensitivity>

A glass substrate (EAGLE XG, 0.7 mm thick (manufactured by Corning)) was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, after spin coating each photosensitive resin composition, at The pre-baking was carried out on a hot plate at 90°C for 120 seconds to volatilize the solvent to form a photosensitive resin composition layer with a film thickness of 3.0 μm.

Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using MPA 5500CF (high-pressure mercury lamp) manufactured by Canon Corporation.

Next, the photosensitive resin composition layer after exposure was developed with an alkaline developing solution (0.4% tetramethylammonium hydroxide aqueous solution) at 23° C. for 60 seconds, and then rinsed with ultrapure water for 20 seconds. The optimal i-ray exposure amount (Eopt) when the 10 μm hole is analyzed by these operations is set as the sensitivity. The lower the value, the more it can be said that the opening is at a low exposure and the sensitivity is high. The evaluation criteria are as follows. Furthermore, it is judged that A~C is in a range where there is no problem in practical application, and D has a problem. The results are shown in Table 3 below.

A: Less than 150mJ/cm ²

B: 150mJ/cm ² or more and less than 300mJ/cm ²

C: 300mJ/cm ² or more and less than 600mJ/cm ²

D: No opening

<transparency>

On a glass substrate exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, spin-coat each photosensitive resin composition, and then perform 120 on a hot plate at 90°C. Pre-bake in seconds to evaporate the solvent to form a photosensitive resin composition layer with a thickness of 3.0 μm.

Then, an ultrahigh-pressure mercury lamp was used to expose the cumulative irradiation amount to 300 mJ/cm ² (energy intensity: 20 mW/cm ² , i-ray), and the substrate was heated at 230° C. for 30 minutes by an oven. The oven was heated at 230°C for 2 hours to obtain a cured film.

The transmittance of the cured film was measured at a wavelength of 400 nm using a spectrophotometer (U-3000: manufactured by Hitachi, Ltd.). The unit is expressed in %. It is judged that A~C is a range where there is no problem in practical application, and D has a problem. The results are shown in Table 3 below.

A: More than 95%

B: Less than 95% and more than 90%

C: Less than 90% and more than 80%

D: less than 80%

[Alignment evaluation]

<alignment>

Each photosensitive resin composition was coated on the substrate by spin coating, pre-dried on a hot plate at 80°C for 1 minute, and calcined in a clean oven at 240°C for 60 minutes to form a cured film with a thickness of 3 μm .

Then, a 1cm×1cm comb-shaped indium tin oxide (ITO) transparent electrode (In Plane Switching (IPS) type that can be connected to the outside is formed by sputtering and dry etching in the center ).

After that, use the ultraviolet polarized light exposure device (HC-2150PUFM, blue technical service LAN (Technical Service) (made by a company) performs optical alignment processing on the substrate using deflected light.

Then, a cell with a cell gap of 3 μm was produced using an epoxy-based sealing material.

The liquid crystal composition for horizontal alignment MLC-2055 manufactured by Merck was injected into the cell, and after the injection port was sealed with a UV-curable sealing agent, a polarizing plate was attached to both sides of the cell according to the alignment direction to produce a liquid crystal display element.

As an evaluation, the alignment of the liquid crystal element was confirmed on a light box (white light source) at a magnification of 20 times of a polarizing microscope, and the condition was evaluated. The evaluation criteria are as follows. The results are shown in Table 3 below.

A: No problem

B: There are shades in the black display

C: There are alignment defects, and bright spots can be seen

D: No alignment, no shading at all

<alignment sensitivity>

In addition, record the sensitivity after the alignment is completed. The evaluation criteria are as follows. The lower the value, the more it can be said that the alignment is completed with low exposure and the alignment sensitivity is high. The results are shown in Table 3 below.

A: Less than 300mJ/cm ²

B: 300mJ/cm ² or more and less than 500mJ/cm ²

C: more than 500mJ/cm ² and less than 1500mJ/cm ²

D: 1500mJ/cm ² or more

[Moisture resistance]

Next, a rectangular wave of ±5 V and 30 Hz was applied to the liquid crystal display element, and it was confirmed that the portion having the transparent electrode of 1 cm×1 cm was blocked (ON/OFF). Make 10 components, put them in a Pressure Cooker Tester (temperature 60°C/90% relative humidity, LH-113 constant temperature and humidity device manufactured by Espec), and confirm The driving situation after 24 hours. The evaluation criteria are as follows. The results are shown in Table 3 below.

A: No change

B: 20% of components have changed

C: 50% of components have changed

D: Not driven

From the results shown in Tables 1 to 3, it can be seen that when the polymer having the constituent unit s1 is not formulated, even if the liquid crystal composition is injected after performing the optical alignment process, the alignment and alignment sensitivity are also poor (comparison Example 1 and Comparative Example 2).

In addition, it can be seen that when other photo-alignment polymers having no structural unit s1 are prepared, the patterning performance is poor (Comparative Example 3 and Comparative Example 4).

On the other hand, it can be seen that the photosensitive resin composition that satisfies at least one of the above Condition 1 to Condition 3 and is provided with a polymer having the constituent unit s1 is aligned in any of the first aspect and the second aspect The alignment sensitivity is good, and it becomes an interlayer insulating film that also serves as an alignment film (Example 1 to Example 53 (first aspect) and Example 54 to Example 74 (second aspect)).

Claims (11)

A photosensitive resin composition comprising: a polymer component A1 containing a polymer A1-1 and a photoacid generator B1, the polymer A1-1 including a group having an acid group protected by an acid-decomposable group A structural unit a1, and the photosensitive resin composition satisfies at least one of the following 1 to 3, 1: The polymer A1-1 further includes a structural unit a2 having a crosslinkable group 2: As the polymer component A1 further contains a polymer A1-2, which contains a structural unit a2 having a crosslinkable group 3: a crosslinking agent C1 having a molecular weight of 1,000 or less having a crosslinkable group and satisfying the following 4 At least one of 5 and 4, 4: The polymer A1-1 or the polymer A1-2 contains the structural unit represented by the following s1 5: As the polymer component A1, it further contains the following s1 The polymer A1-3 s1 of the structural unit of: structural unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton and an alkyl group having 10 to 30 carbon atoms, and having optical alignment The structural unit of the sex group has a content of the polymer having the structural unit represented by s1 relative to the total solid content of the composition of 0.1% by mass to 20% by mass. The photosensitive resin composition as described in item 1 of the patent application range, wherein the acid group is protected by an acid-decomposable group in which the acid group is protected in the form of an acetal. A photosensitive resin composition comprising: a polymer component A2 containing a polymer A2-1 and a quinonediazide compound B2, the polymer A2-1 includes a structural unit a3 having an acid group, and the photosensitive The resin composition satisfies at least one of the following 1 to 3, 1: the polymer A2-1 further contains a structural unit a2 having a crosslinkable group 2: the polymer component A2 further contains a polymer A2- 2. The polymer A2-2 contains a structural unit a2 having a crosslinkable group 3: It further contains a crosslinking agent C2 having a crosslinkable group and a molecular weight of 1,000 or less and satisfies at least one of the following 4 and 5, 4: The polymer A2-1 or the polymer A2-2 includes the structural unit 5 represented by the following s1: as the polymer component A2, a polymer A2- that includes the structural unit represented by the following s1 is further included 3 s1: a structural unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton, and an alkyl group having 10 to 30 carbon atoms, and a structural unit having a photo-alignment group, where the relative For the total solid content of the composition, the content of the polymer having the structural unit represented by s1 is 0.1% by mass to 20% by mass. The photosensitive resin composition according to any one of claims 1 to 3, wherein the photo-alignment group is a group imparted with alignment by a photodimerization reaction. Photosensitive as described in any of items 1 to 3 of the patent application Resin composition, wherein the photo-alignment group is a cinnamate group or a chalcone group. The photosensitive resin composition according to any one of claims 1 to 3, wherein the crosslinkable group is an epoxy group or an oxetanyl group. The photosensitive resin composition according to any one of claims 1 to 3, wherein s1 is at least one part selected from the group consisting of a fluorine-substituted hydrocarbon group and a siloxane skeleton Constituent units of the structure, and constituent units with photo-alignment groups. The photosensitive resin composition according to any one of claims 1 to 3, which contains an organic solvent D. A method for manufacturing a cured film, comprising: the step of applying the photosensitive resin composition as described in item 8 of the patent application to a substrate; the step of removing the organic solvent D from the applied photosensitive resin composition A step of exposing the photosensitive resin composition from which the organic solvent D has been removed by active radiation; a step of developing the exposed photosensitive resin composition with a developing solution; and a step of developing the photosensitive resin composition The step of heat curing to obtain a cured film. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 8. A liquid crystal display device having a patent application as the 10th item The hardened film.